Mesogenic compounds, medium for electro-optical displays and electro-optical display

ABSTRACT

The instant invention relates to liquid crystal media comprising a strongly dielectrically positive component A, comprising one or more compounds of formula I  
                 
wherein the parameters have the meanings given in the text. It also relates to the compounds as such and to mesogenic or liquid crystalline mixtures comprising these compounds.

FIELD OF THE INVENTION

The present invention relates to mesogenic compounds, media forelectro-optical displays comprising these and to electro-opticaldisplays comprising these media, in particular to displays usingmesogenic modulation media which are in an optically isotropic state atthe temperature of operation of the light modulation elements and torespective modulation elements and displays.

PROBLEM TO BE SOLVED AND STATE OF THE ART

Liquid Crystal Displays (LCDs) are widely used to display information.Electro-optical modes employed are e.g. the twisted nematic (TN)-, thesuper twisted nematic (STN)- and the electrically controlledbirefringence (ECB)-mode with their various modifications, as well asothers. Besides these modes, which all do use an electrical field, whichis substantially perpendicular to the substrates, respectively to theliquid crystal layer, there are also electro-optical modes employing anelectrical field substantially parallel to the substrates, respectivelythe liquid crystal layer like e.g. the in-plane switching (IPS)-mode(compare e.g. DE 40 00 451 and EP 0 588 568).

Besides the various different modes using the liquid crystal medium assuch, oriented on surfaces, which typically are pre-treated to achieveuniform alignment of the liquid crystal material, there are applicationsusing composite systems of liquid crystal materials of low molecularweight together with polymeric materials such as e.g. polymer dispersedliquid crystal (PDLC)-, nematic curvilinearily aligned phase (NCAP)- andpolymer network (PN)-systems, as disclosed for example in WO 91/05 029.These composite systems typically use an electrical field substantiallyperpendicular to the composite layer.

LCDs are used for direct view displays, as well as for projection typedisplays. Besides these applications LCDs, especially LCDs comprisingcomposite systems like PDLCs and in particular so called holographicPDLC (HPDLC) systems are used in practical applications. HPDLCs aredescribed e.g. in Date, Takeuchi, Tanaka, and Kato, Journal of the SID7/1 (1999), p. 17 to 22, which is incorporated by reference. These HPDLCdisplays are generating three bright colours, preferably primary colors,utilizing Bragg reflection. This technique results in excellent brightcolours, as it does neither need polarizers, nor color filters. A singlelayer of the periodic structure of polymer and liquid crystal controlsthe reflection of one particular colour. To realise three primary colorsconsequently three layers, one for each colour are required. Each of thethree layers has to be addressed independently. This requires three setsof HPDLC films, each with corresponding electrodes. This large number oflayers and corresponding electrodes, which is difficult to realize witha good yield in mass production, can beneficiously be reduced when the“two-frequency” drive method is applied.

For composite systems a high Δn of the liquid crystal used is requiredin order to achieve an efficiently scattering state and to realize agood contrast. Though there have been proposed PDLC-systems with liquidcrystal mixtures with low Δn to improve the so called off axis haze, thepredominant problem in most cases is to achieve sufficient contrast inthe first place. This is especially the case for PDLC-systems, which aredisclosed e.g. in Date, Takeuchi, Tanaka, and Kanto, Journal of the SID7/1 (1999), p. 17-22. The liquid crystals available typically arecharacterized by Δn values of up to 0.280 or even up to 0.29. This upperlimit, however, is still insufficiently low for many applications.Further it has so far only been achieved accepting various compromiseswith respect to the other properties of the liquid crystal mixturesused. The most typical undesired trade-offs are an insufficiently highclearing point, an unfavourably narrow nematic phase range, a ratherhigh temperature for the lower end of the stability of the nematicphase, too low dielectric anisotropy and hence too high operatingvoltages, unfavourable elastic constants and last not least too highviscosity values or combinations thereof.

Good compatibility with the precursors of the polymers of the compositesystems and easy phase separation during the formation of the compositesystems are obvious prerequisites for liquid crystals for suchapplications.

Another promising electro-optical mode used in LCDs is the opticallycompensated bent (OCB) mode. This mode is described e.g. in Yamaguchi etal., “Wide-Viewing-Angle Display Mode for the Active-Matrix LCD UsingBend-Alignment Liquid-Crystal Cell”, SID 93, Digest, p. 277 (1993).

This mode is very promising. It is particularly well suited for directview applications, as it is characterised by a favourable viewing angledependence. Also the response times are quite short. However for videorate response for the display of changing grey shades the response timestill needs to be improved. Compared to a conventional TN display, in anOCB display the amount of deformation of the director is much smaller.Whereas in a TN display the director is oriented almost parallel to thesubstrates in the non-powered state and changes its direction to almostperpendicular to the substrates upon application of the driving voltage,in an OCB display the director orientation changes to the same finalorientation, but it does start from an already almost homeotropic bentstarting configuration. Thus, a higher birefringence of the liquidcrystal media used is required.

Recently light controlling elements and displays using mesogenicmodulation media which are in an optically isotropic state at thetemperature of operation of the light modulation elements and torespective modulation elements and display have been described. DE 10217 273 A1 as well as DE 162 41 301.0, DE 102 53 325.3 and DE 102 52250.2, all yet to be laid open except the first one, describe lightcontrolling elements using modulation media which are in the isotropicstate at the operation temperature of the elements, whereas DE 103 13979.6, also yet to be laid open, describes elements using modulationmedia which are in the optically isotropic blue phase, when operated.This type of light modulation elements is characterised by very fastresponse times and by an excellent contrast with minimal viewing angledependence. However, especially in this novel type of light modulationelements and displays the temperature range of operation has not beensufficiently wide so far and the temperature dependence of the operationvoltages still is quite high and has to be reduced in order to alloweasier addressing over a wider range of temperatures.

The compounds should be suitable for use in mesogenic media inelectro-optical displays, in particular as control media of thesedisplays. For this purpose they should be soluble in base media with amesogenic phase, e.g. a nematic, cholesteric, smectic or even a mediumhaving an optically isotropic phase, e.g. a blue phase. Preferably theyeven should exhibit one or more of these phases as single compounds.

These compounds should lead to a decrease of the operation voltages ofthe corresponding electro-optical displays and of its temperaturedependency. Further they should not reduce the voltage holding ratio ofthe media too much, in order to allow for addressing of the displays bya matrix of active elements with a non-linear electric responsecharacteristic, i.e. in an active matrix display.

Liquid crystalline or mesogenic compounds with very high values of thedielectric anisotropy so far have mostly (with only very few exceptions)been realised by incorporation of strongly polar terminal groupsespecially such as a cyano (—CN) group or also a isothiocyanato (—NCS)group as e.g. in EP 01 101 157. Use of compounds of these types,however, leads to mesogenic media, especially for use in TN typedisplays, with rather low specific resistivity, which in turn do notmatch the demanding requirements for the voltage holding ratio of themedia in displays driven by an active matrix, as e.g. The respectivefunctional or modulation media used for the displays are disclosed in DE102 17 273 A1.

In contrast, mesogenic media consisting predominantly or even entirelyof mesogenic compounds with a terminal fluorine substitution or with afluorinated terminal group, so far, do not provide a dielectricanisotropy, which is high enough to realise low operation voltages,especially if they are used in light modulation media for the displaysdisclosed in DE 102 17 273 which are most demanding in this respect.

Mesogenic compounds with two lateral alkoxy groups like e.g.

have been hinted at in U.S. Pat. No. 6,177,154. The compounds realisedso far, however, do not show the extremely high values for thedielectric anisotropy and/or the optical anisotropy required here. Thesecompounds further are not particularly reliable and neither are readilyavailable (i.e. rather difficult to prepare), nor particularly wellsoluble. Thus, there is a significant need for liquid crystal media withsuitable properties for practical applications such as a very highdielectric anisotropy, a suitably wide nematic phase range or at leastsufficient mesogenity for use in practical media, low viscosities,appropriate optical anisotropy Δn according to the display mode used,which also are readily accessible.

Further the media used so far for the displays disclosed in DE 102 17273 A1 and in DE 103 13 979.6 all tend to lead to rather pronouncedtemperature dependence of the characteristic voltages.

Present Invention

Surprisingly, it now has been found that mesogenic media with high Asespecially useful for displays disclosed in DE 102.17 273 A1 and inparticular in DE 103 13 979.6 can be realised, which do not exhibit thedrawbacks of the materials of the prior art, or at least do exhibit themto a significantly lesser degree.

Last not least, the compounds of the instant invention are particularlywell suited for use in light modulation elements and displays using amodulation medium which is in an optically isotropic state, preferablyin the blue phase, as disclosed in DE 103 13 979.6. In these displaysthe inventive compounds do lead to a significant decrease of thetemperature dependence of the characteristic voltages and hence of theoperation voltages and/or to a significant increase of the temperaturerange over which the temperature dependence is rather small.

These improved liquid crystal media according to the instant applicationare realized by using at least two components: a first liquid crystalcomponent (called component A) comprising compounds of formula I, whichare strongly dielectrically positive compounds with very high values ofΔs and also Δn

wherein

-   a, b, c and d are independently of each other 0, 1 or 2, whereby a+b    c d≦4;-   R¹¹ is hydrogen, an alkyl or alkoxy radical having from 1 to 15    carbon atoms, wherein one or more methylene groups of said alkyl or    alkoxy radical may be replaced independently of each other by —O—,    —S—, —SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or —O—CO— such that    oxygen and/or sulfur atoms are not linked directly to each other,    said alkyl or alkoxy radical being unsubstituted or mono-substituted    with a —CN group or mono- or poly-substituted with halogen; or aryl,    aryloxy, alkylaryl, alkylaryloxy, alkylarylalkyl, alkylarylalkoxy,    cycloalkyl, cycloalkyloxy, cycloalkylalkenyloxy, alkylcycloalkyl,    alkylcycloalkyloxy or alkylcycloalkylalkenyloxy, each with up to 15    carbon atoms, wherin said in radicals being unsubstituted or    mono-substituted with a —CN group or mono- or poly-substituted with    halogen one ore more ═CH— groups may be replaced independently of    each other by ═N— and/or one more —CH₂— groups may be replaced    independently of each other by —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—,    —C≡C—, —CO—O— and/or —O—CO— such that nitrogen and oxygen and/or    sulfur atoms are not linked directly to each other;-   L¹¹, L¹², L¹³ and L¹⁴ are, independently of each other, hydrogen, an    alkyl or alkoxy radical having from 1 to 15 carbon atoms, wherein    one or more methylene groups of said alkyl or alkoxy radical may be    replaced independently of each other by —O—, —S—, —SiR^(x)R^(y)—,    —CH═CH—, —C≡C—, —CO—O— and/or —O—CO— such that oxygen and/or sulfur    atoms are not linked directly to each other, said alkyl or alkoxy    radical being unsubstituted or mono-substituted with a —CN group or    mono- or poly-substituted with halogen; or aryl, aryloxy, alkylaryl,    alkylaryloxy, alkylarylalkyl, alkylarylalkoxy, cycloalkyl,    cycloalkyloxy, cycloalkylalkenyloxy, alkylcycloalkyl,    alkylcycloalkyloxy or alkylcycloalkylalkenyloxy, each with up to 15    carbon atoms, wherin said in radicals being unsubstituted or    mono-substituted with a —CN group or mono- or poly-substituted with    halogen one ore more ═CH— groups may be replaced independently of    each other by ═N— and/or one more —CH₂— groups may be replaced    independently of each other by —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—,    —C≡C—, —CO—O— and/or —O—CO— such that nitrogen and oxygen and/or    sulfur atoms are not linked directly to each other,    -   whereby preferably    -   L¹³ and L¹⁴ are hydrogen, if at least one of L¹¹ and L¹² is not        hydrogen;    -   L¹¹ and L¹² are hydrogen, if at least one of L¹³ and    -   L¹⁴ is not hydrogen;    -   at least one of L¹¹, L¹², L¹³ and L¹⁴ is not hydrogen; and    -   L¹¹ and L¹² are not halogen at the same time;-   X¹¹ is H, halogen, —CN, —NCS, —SF₅, —S—R^(z), —SO₂—R^(z), an alkyl    or alkoxy radical having from 1 to 15 carbon atoms, wherein one or    more methylene groups of said alkyl or alkoxy radical may be    replaced independently of each other by —O—, —S—, —SiR^(x)R^(y)—,    —CH═CH—, —C≡C—, —CO—O— and/or —O—CO— such that oxygen and/or sulfur    atoms are not linked directly to each other, said alkyl or alkoxy    radical being unsubstituted or mono-substituted with a —CN group or    mono- or poly-substituted with halogen; or aryl, aryloxy, alkylaryl,    alkylaryloxy, alkylarylalkyl, alkylarylalkoxy, cycloalkyl,    cycloalkyloxy, cycloalkylalkenyloxy, alkylcycloalkyl,    alkylcycloalkyloxy or alkylcycloalkylalkenyloxy, each with up to 15    carbon atoms, wherin said in radicals being unsubstituted or    mono-substituted with a —CN group or mono- or poly-substituted with    halogen one ore more ═CH— groups may be replaced independently of    each other by ═N— and/or one more —CH₂— groups may be replaced    independently of each other by —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—,    —C≡C—, —CO—O— and/or —O—CO— such that nitrogen and oxygen and/or    sulfur atoms are not linked directly to each other;-   R^(x) and R^(y) are independently of each other hydrogen or an alkyl    radical having from 1 to 7 carbon atoms;-   R^(z) is an alkyl radical having from 1 to 7 carbon atoms, said    alkyl radical being unsubstituted or mono- or poly-substituted with    halogen;-   A¹¹, A¹², A¹³ and A14 are independently of each other a ring of one    of the following formulas:    whereby each of A¹¹, A¹², A¹³ and A¹⁴ may be the same ring or two    different rings if present more than once;-   Y¹¹, Y¹², Y¹³ and Y¹⁴ are independently of each other hydrogen,    halogen, an alkyl or alkoxy radical having from 1 to 15 carbon atoms    wherein one or more methylene groups of said alkyl or alkoxy radical    may be replaced independently of each other by —O—, —S—,    —SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or —O—CO-such that oxygen    and/or sulfur atoms are not linked directly to each other, said    alkyl or alkoxy radical being unsubstituted or mono- or    poly-substituted with halogen; or aryl, aryloxy, alkylaryl,    alkylaryloxy, alkylarylalkyl, alkylarylalkoxy, cycloalkyl,    cycloalkyloxy, cycloalkylalkenyloxy, alkylcycloalkyl,    alkylcycloalkyloxy or alkylcycloalkylalkenyloxy, each with up to 15    carbon atoms, wherin said in radicals being unsubstituted or    mono-substituted with a —CN group or mono- or poly-substituted with    halogen one ore more ═CH— groups may be replaced independently of    each other by ═N— and/or one more —CH₂— groups may be replaced    independently of each other by —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—,    —C≡C—, —CO—O— and/or —O—CO— such that nitrogen and oxygen and/or    sulfur atoms are not linked directly to each other;-   f, g, h and j are independently of each other 0, 1, 2 or 3;-   Z¹¹, Z¹², Z¹³ and Z¹⁴ are independently of each other a single bond,    —CH₂CH₂—, (—CH₂CH₂—)₂, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—,    —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—,    —CO—O— or —O—CO— whereby each of Z¹¹, Z¹², Z¹³ and Z¹⁴ may have the    same or a different meaning if present more than once,    and preferably of its sub-formula I-1

Wherein the parameters are as defined above and preferably

-   R¹¹, R¹² and R¹³, independently of each other, are n-alkyl or    n-alkoxy with 1 to 20, preferably 1 to 10, preferably 1 to 8,    preferably 2 to 8, preferably 2 to 6 C-atoms, alkenyl, alkenyloxy or    alkoxyalkyl with 2 to 20, preferably 2 to 8, preferably 2 to 6,    preferably 2 to 5 C-atoms or CN, NCS, halogen, preferably F, Cl,    halogenated alkyl, alkenyl or alkoxy, preferably mono-, di- or    oligo-fluorinated alkyl, alkenyl or alkoxy, especially preferred CF₃    OCF₂H or OCF₃, preferably R¹¹, R¹² and R¹³ are alkoxy, preferably    with 1 to 10 C-atoms,-   L¹¹, L¹², Y¹¹ and Y¹², independently of each other, are H, halogen,    preferably F or Cl, CN, NCS, unsubstituted or halogenated alkyl,    alkenyl, alkoxy, aryl, aryloxy, alkylaryl, alkylaryloxy,    alkylarylalkyl, alkylarylalkoxy, cycloalkyl, cycloalkyloxy,    cycloalkylalkenyloxy, alkylcycloalkyl, alkylcycloalkyloxy or    alkylcycloalkylalkenyloxy, each with up to 15 carbon atoms, wherin    said in radicals being unsubstituted or mono-substituted with a —CN    group or mono- or poly-substituted with halogen one ore more ═CH—    groups may be replaced independently of each other by ═N— and/or one    more —CH₂— groups may be replaced independently of each other by    —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or —O—CO— such    that nitrogen and oxygen and/or sulfur atoms are not linked directly    to each other, preferably mono-, di- or oligo-fluorinated alkyl,    alkenyl or alkoxy, especially preferred CF₃, OCF₂H or OCF₃,    preferably F or Cl, halogenated alkyl, alkenyl or alkoxy, preferably    mono-, di- or oligo-fluorinated alkyl, alkenyl or alkoxy, especially    preferred CF₃, OCF₂H or OCF₃, preferably at least one of L¹¹ and R¹²    is, most preferably both are F and Y¹¹ and Y¹², independently of    each other, preferably H or F and-   X¹¹ is H, halogen, preferably F or Cl, CN, NCS, SF₅, —SCF₃, —SO₂CF₃,    —SO₂C₂F₅, —SO₂C₄F₉, unsubstituted or halogenated alkyl, alkenyl,    alkoxy, aryl, aryloxy, alkylaryl, alkylaryloxy, alkylarylalkyl,    alkylarylalkoxy, cycloalkyl, cycloalkyloxy, cycloalkylalkenyloxy,    alkylcycloalkyl, alkylcycloalkyloxy or alkylcycloalkylalkenyloxy,    each with up to 15 carbon atoms, wherin said in radicals being    unsubstituted or mono-substituted with a —CN group or mono- or    poly-substituted with halogen one ore more ═CH— groups may be    replaced independently of each other by ═N— and/or one more —CH₂—    groups may be replaced independently of each other by —O—, —S—,    —SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or —O—CO— such that    nitrogen and oxygen and/or sulfur atoms are not linked directly to    each other, preferably mono-, di- or oligo-fluorinated alkyl,    alkenyl or alkoxy, preferably F or Cl, CN, unsubstituted or    halogenated alkyl, alkenyl or alkoxy, preferably mono-, di- or    oligo-fluorinated alkyl, alkenyl or alkoxy, especially preferred F,    CF₃ or OCF₃.

In a preferred embodiment of the present invention, one or more of thegroups R¹¹, L¹¹ L¹², L¹³, L¹⁴, Y¹¹, Y¹², Y¹³, Y¹⁴ and X¹¹, which arepresent in the compounds of formula I, is/are a chiral group, whichpreferably is a group of formula I*

wherein

-   Q¹ is an alkylene or alkylene-oxy group with 1 to 9 C atoms or a    single bond,-   Q² is an alkyl or alkoxy group with 1 to 10 C atoms which may be    unsubstituted, mono- or polysubstituted by F, Cl, Br or CN, it being    also possible for one or more non-adjacent CH₂ groups to be    replaced, in each case independently from one another, by —C≡C—,    —O—, —S—, —NH—, —N(CH₃)—, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO— or    —CO—S— in such a manner that oxygen atoms are not linked directly to    one another,-   Q³ is F, Cl, Br, CN or an alkyl or alkoxy group as defined for Q²    but being different from Q².

In case Q¹ in formula I* is an alkylene-oxy group, the O atom ispreferably adjacent to the chiral C atom.

Preferred chiral groups of formula I* are 2-alkyl, 2-alkoxy,2-methylalkyl, 2-methylalkoxy, 2-fluoroalkyl, 2-fluoroalkoxy,2-(2-ethin)-alkyl, 2-(2-ethin)-alkoxy, 1,1,1-trifluoro-2-alkyl and1,1,1-trifluoro-2-alkoxy.

Particularly preferred chiral groups I* are 2-butyl (=1-methylpropyl),2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl,2-propylpentyl, in particular 2-methylbutyl, 2-methylbutoxy,2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy,2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl,2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methoxyoctoxy,6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxycarbonyl,2-methylbutyryloxy, 3-methylvaleroyloxy, 4-methylhexanoyloxy,2-chlorpropionyloxy, 2-chloro-3-methylbutyryloxy,2-chloro-4-methylvaleryloxy, 2-chloro-3-methylvaleryloxy,2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl, 1-methoxypropyl-2-oxy,1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy,2-fluorooctyloxy, 2-fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy,1,1,1-trifluoro-2-octyl, 2-fluoromethyloctyloxy for example. Verypreferred are 2-hexyl, 2-octyl, 2-octyloxy, 1,1,1-trifluoro-2-hexyl,1,1,1-trifluoro-2-octyl and 1,1,1-trifluoro-2-octyloxy.

In addition, compounds containing an achiral branched alkyl group mayoccasionally be of importance, for example, due to a reduction in thetendency towards crystallization. Branched groups of this type generallydo not contain more than one chain branch. Preferred achiral branchedgroups are isopropyl, isobutyl (=methylpropyl), isopentyl(=3-methylbutyl), isopropoxy, 2-methyl-propoxy and 3-methylbutoxy.

In a further preferred embodiment, which may be different or identicalto the previously described embodiments, at least one and preferably oneof the rings A¹¹, A¹², A¹³ and A¹⁴, which are present in the compound offormula 1 is a chiral moiety, preferably selected from the group ofcholesterine-diyl, pinimenthol-diyl and tetrahydropyrane-diyl and mostpreferably tetrahydropyrane-diyl.

In a further preferred embodiment of the present invention, which may bedifferent or identical to the previously described embodiments, one ormore of the groups R¹¹, L¹¹, L¹², L¹³, L¹⁴, Y¹¹, Y¹², Y¹³, Y¹⁴ and X¹¹,which are present in the compounds of formula I, is/are PG-SG wherein

SG is a spacer group and

PG is a polymerisable or reactive group.

The polymerisable or reactive group PG is preferably selected fromCH₂═CW¹—COO—,

CH₂═CW²—(O)_(k1)—, CH₃—CH≡CH—O—, (CH₂═CH)₂CH—OCO—, (CH₂═CH—CH₂)₂CH—OCO—,(CH₂═CH)₂CH—O—, (CH₂═CH—CH₂)₂N—, HO—CW²W³—, HS—CW²W³—, HW²N—,HO—CW²W³—NH—, CH₂═CW¹—CO—NH—, CH₂═CH—(COO)_(k1)—Phe-(O)_(k2)—,Phe-CH═CH—, HOOC—, OCN—, and W⁴W⁵W⁶Si—, with W¹ being H, Cl, CN, phenylor alkyl with 1 to 5 C-atoms, in particular H, C₁ or CH₃, W² and W³being independently of each other H or alkyl with 1 to 5 C-atoms, inparticular methyl, ethyl or n-propyl, W⁴, W⁵ and W⁶ being independentlyof each other Cl, oxaalkyl or oxacarbonylalkyl with 1 to 5 C-atoms, Phebeing 1,4-phenylene and k₁ and k₂ being independently of each other 0 or1.

Especially preferably PG is a vinyl group, an acrylate group, amethacrylate group, an oxetane group or an epoxy group, especiallypreferably an acrylate or methacrylate group.

As for the spacer group SG all groups can be used that are known forthis purpose to those skilled in the art. The spacer group SG ispreferably of formula SG′-X, such that PG-SG- is PG-SG′-X—, wherein

-   SG′ is alkylene with up to 20 C atoms which may be unsubstituted,    mono- or poly-substituted by F, Cl, Br, I or CN, it being also    possible for one or more non-adjacent CH₂ groups to be replaced, in    each case independently from one another, by —O—, —S—, —NH—, —NR⁰¹—,    —SiR⁰¹R⁰²—, —CO—, —COO—, —OCO—, —OCO—O—, —S—, —CO—, —CO—S—, —CH═CH—    or —C≡C— in such a manner that O and/or S atoms are not linked    directly to one another,-   X is —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR⁰¹—, —NR⁰¹—CO—,    —OCH₂—, —CH₂O—, —SCH₂—, —CH₂S—, —CF₂O—, —OCF₂—, —CF₂S—, —SCF₂—,    —CF₂CH₂—, —CH₂CF₂—, —CF₂CF₂—, —CH═N—, —N═CH—, —N═N—, —CH═CR⁰¹—,    —CY⁰¹═CY⁰²—, —C≡C—, —CH═OH—OOO—, —OCO—, —CH═CH— or a single bond,    and-   R⁰¹, R⁰², Y⁰¹ and Y⁰² have one of the respective meanings given    above.-   X is preferably —O—, —S—, —OCH₂—, —CH₂O—, —SCH₂—, —CH₂S—, —CF₂O—,    —OCF₂—, —CF₂S—, —SCF₂—, —CH₂CH₂—, —CF₂CH₂—, —CH₂CF₂—, —CF₂CF₂—,    —CH═N—, —N═CH—, —N═N—, —CH═CR⁰—, —CY⁰²═CY⁰²—, —C≡C— or a single    bond, in particular —O—, —S—, —C≡C—, —CY⁰¹═CY⁰²— or a single bond,    very preferably a group that is able to from a conjugated system,    such as —C≡C— or —Cy⁰¹═CY⁰²—, or a single bond.

Typical groups SG′ are, for example, —(CH₂)_(p)—,—(CH₂CH₂O)_(q)—CH₂CH₂—, —CH₂CH₂—S—CH₂CH₂— or —CH₂CH₂—NH—CH₂CH₂— or—(SiR⁰R⁰⁰—O)_(p)—, with p being an integer from 2 to 12, q being aninteger from 1 to 3 and R⁰, R⁰⁰ and the other parameters having themeanings given above.

Preferred groups SG′ are ethylene, propylene, butylene, pentylene,hexylene, heptylene, octylene, nonylene, decylene, undecylene,dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene,ethylene-thioethylene, ethylene-N-methyl-iminoethylene,1-methylalkylene, ethenylene, propenylene and butenylene for example.

In another preferred embodiment SG′ is a chiral group of formula I*′:

wherein

-   Q¹ and Q³ have the meanings given in formula I*, and-   Q⁴ is an alkylene or alkylene-oxy group with 1 to 10 C atoms or a    single bond, being different from Q¹,-   with Q¹ being linked to the polymerisable group PG.

Further preferred are compounds with one or two groups PG-SG- wherein SGis a single bond.

In case of compounds with two groups PG-SG, each of the twopolymerisable groups PG and the two spacer groups SG can be identical ordifferent.

In a preferred embodiment of the instant are compounds of formula Iwherein at one or more, preferably two, three or more, of the radicals

-   R¹¹, L¹¹, L¹², L¹³, L¹⁴, Y¹¹, Y¹², Y¹³, Y¹⁴ and X¹¹, which are    resent, is/are aryl, aryloxy, alkylaryl, alkylaryloxy,    alkylarylalkyl, alkylarylalkoxy, cycloalkyl, cycloalkyloxy,    cycloalkylalkenyloxy, alkylcycloalkyl, alkylcycloalkyloxy or    alkylcycloalkylalkenyloxy, preferably aryloxy, alkylaryloxy,    cycloalkyloxy, cycloalkylalkenyloxy, alkylcycloalkyloxy or    alkylcycloalkylalkenyloxy, each with up to 15 carbon atoms, wherin    said in radicals being unsubstituted or mono-substituted with a —CN    group or mono- or poly-substituted with halogen one ore more ═CH—    groups may be replaced independently of each other by ═N— and/or one    more —CH₂— groups may be replaced independently of each other by    —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or —O—CO— such    that nitrogen and oxygen and/or sulfur atoms are not linked directly    to each other.

Preferably one or more, preferably two, three or more, of the radicals

-   R¹, L¹¹, L¹², L¹³, L¹⁴, Y¹¹, Y¹², Y¹³, Y¹⁴ and X¹¹, which are    present,    -   is/are selected from the group of radicals:        and wherein-   R^(x) has the meaning given above and preferably is n-alkyl and most    preferably methyl.

Preferably the mesogenic media according to the present inventionsimultaneously comprise a second mesogenic, liquid crystalline component(called component B), which is a dielectrically positive componentcomprising, and preferably consisting of terminally polar substitutedbi- or terphenyl compounds, which or some of which optionally arelaterally fluorinated, preferably of formula II

wherein

-   n² is 0, 1, 2 or 3,-   R² has the meaning given for R¹¹ under formula I, preferably under    formula I-1 above, but preferably is alkyl or alkenyl,-   Z²¹ and Z²², independently of each other, are a single bond,    —CH₂CH₂—, (—CH₂CH₂—)₂, —CF₂—CF₂, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—,    —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—,    —CO—O— or —O—CO— (whereby each of Z²² may have the same or a    different meaning if present more than once), preferably a single    bond, —C≡C—, —CF₂O— or —CO—O—, especially a single bond,-    each, independently of each other, are-    whereby-    also may be    and-   X² is CN, SF₅, SO₂CF₃, NCS, CF₃, OCF₃, F or Cl, preferably CN, NCS    or Cl, most preferably CN or NCS.

Preferably the mesogenic media according to the instant inventioncontain a component A comprising, preferably predominantly consisting ofand most preferably entirely consisting of compounds of formula I.

The compounds of formula I, wherein at least one of L¹¹ and L¹² is Fand/or wherein at least one of Y¹¹ and Y¹² is F are preferred

Liquid crystal compounds in this application embrace compounds with aliquid crystalline phase by themselves as well as compounds, which arecompatible with mesogenic phases, especially with the nematic phase,without decreasing the clearing point unacceptably. The latter compoundshave a mesogenic structure and are also called mesogenic compounds.

The compounds of formula I can be prepared according to the followingreaction schemes, Scheme 1 to 4, or variants thereof which will beeasily recognized by the person skilled in the art.

wherein

-   R, R′ and R″, independently from each other, are alkyl, alkoxy,    alkenyl, alkenyloxy or oxaalkyl, preferably alkoxy, preferably R′    and R″ and most preferably R, R′ and R″ are identical to each other,    and-   Y¹¹ and Y¹², independently of each other, are as defined    hereinbefore.    wherein R and X¹¹ is as defined above and R′″ is other, alkyl,    alkenyl, alkenyloxy, oxaalkenyl or oxaalkyl. It should be noted that    —OR′″ radicals having different meanings for R′″ can easily be    introduced by stepwise reaction of    with (1) 1 equivalent of an alcohol R′″^(a)—OH in the presence of    NaH at a reaction temperature of about 80° C. and (2)1 equivalent of    an alcohol R′″^(b)—OH in the presence of NaH at a reaction    temperature of about 120° C.    wherein R¹¹, L¹¹ and L¹² are as defined hereinbefore and X is H or    F.    wherein R¹¹, L¹¹, L¹² have the same meaning as given above for    general formula I.

Comprising in this application means in the context of compositions thatthe entity referred to, e.g. the medium or the component, contains thecompound or compounds in question, preferably in a total concentrationof 10% or more and most preferably of 20% or more.

Predominantly consisting, in this context, means that the entityreferred to contains 80% or more, preferably 90% or more and mostpreferably 95% or more of the compound or compounds in question.

Entirely consisting, in this context, means that the entity referred tocontains 98% or more, preferably 99% or more and most preferably 100.0%of the compound or compounds in question.

The compounds of formula I are preferably selected from the group ofsub-formulae I-1.1 to I-1.15, especially I-1.1, I-1.2, I-1.3, I-1.4and/or I-1.5:

wherein the parameters have the respective meanings given under formulaI above and preferably

-   R¹¹ to R¹³ are identical to each other and preferably are alkoxy,    alkenyloxy, halogenated alkoxy or oxaalkoxy, and-   Y¹¹ and Y¹² are independently of each other H, CF₃ or F.

The compounds of formulae I-1.1 to I-1.5 preferably are selected fromthe group of compounds of formula I-1A

whereinR, R′, R″ X, Y¹¹ and Y¹² are as defined above, preferablyX is F, CF₃, SF₅, SO₂CF₃, OCF₃ or CN andY¹¹ and Y¹² are independently of each other H, CF₃ or F.

Likewise compounds of formula I-1A having only one or no F substituentat the middle phenyl ring are preferred as well.

In a preferred embodiment the liquid crystalline media according to theinstant invention contains a component B comprising, preferablypredominantly consisting of compounds of formula II as defined hereinbefore.

Preferably in these compounds of formula II

-   R² is alkyl or alkoxy, wherein one or more methylene groups of said    alkyl may be replaced —C≡C—, and for sub-formulae IIb and IIc    preferably alkyl.

Additionally the media according to the present invention may contain acomponent C. This component C may be dielectrically neutral ordielectrically negative, depending upon the relative amounts ofcompounds with positive and negative dielectrical anisotropy containedtherein.

Component C is used in a concentration of 0 to 40%, preferably 0 to 20%and most preferably from 0 to 10% of the total mixture.

Optionally the inventive liquid crystal medium contains a furthercomponent D, which is a dielectrically neutral component and preferablycomprises and more preferably consists of dielectrically neutralcompounds.

Component D is used to adjust especially the phase range and the opticalanisotropy of the inventive liquid crystal media.

The concentration of component D in the liquid crystal medium accordingto the present invention is preferably 0% to 40%, more preferably 0% to25%, most preferably 0% to 15% and in particular 3 to 10%.

Optionally the inventive liquid crystal medium contains a furthercomponent E, which is a chiral component and preferably comprises andmore preferably consists of chiral compounds. It is preferred that theliquid crystal medium according to the invention contains that furtherchiral component E.

Optionally, the inventive media can comprise further liquid crystalcompounds in order to adjust the physical properties. Such compounds areknown to the expert. Their concentration in the media according to theinstant invention is preferably 0 to 30%, more preferably 0 to 20% andmost preferably 5 to 15%.

Preferably the liquid crystal medium contains 50% to 100%, morepreferably 70% to 100% and most preferably 80% to 100% and in particular90% to 100% totally of components A and B which contain, preferablypredominantly consist of and most preferably entirely consist of one ormore of compounds of formulae I and II, respectively.

In the present application the term dielectrically positive compoundsdescribes compounds with Δε>1,5, dielectrically neutral compounds arecompounds with −1,5≦Δε≦1,5 and dielectrically negative compounds arecompounds with Δε<−1,5. The same holds for components. Δε is determinedat 1 kHz and 20° C. The dielectrical anisotropies of the compounds isdetermined from the results of a solution of 10% of the individualcompounds in a nematic host mixture. The capacities of these testmixtures are determined both in a cell with homeotropic and withhomogeneous alignment. The cell gap of both types of cells isapproximately 10 μm. The voltage applied is a rectangular wave with afrequency of 1 kHz and a root mean square value typically of 0.1V or 0.5V to 1.0 V, however, it is always selected to be below the capacitivethreshold of the respective test mixture.

For dielectrically positive compounds the mixture ZLI-4792 and fordielectrically neutral, as well as for dielectrically negativecompounds, the mixture ZLI-3086, both of Merck KGaA, Germany are used ashost mixture, respectively. The dielectric permittivities of thecompounds are determined from the change of the respective values of thehost mixture upon addition of the compounds of interest and areextrapolated to a concentration of the compounds of interest of 100%.

Components having a nematic phase at the measurement temperature of 20°C. are measured as such, all others are treated like compounds.

The term threshold voltage refers in the instant application to theoptical threshold and is given for 10% relative contrast (V₁₀) and theterm saturation voltage refers to the optical saturation and is givenfor 90% relative contrast (V₉₀) both, if not explicitly statedotherwise. The capacitive threshold voltage (V₀, also calledFreedericks-threshold V_(Fr)) is only used if explicitly mentioned.

The ranges of parameters given in this application are all including thelimiting values, unless explicitly stated otherwise.

Throughout this application, unless explicitly stated otherwise, allconcentrations are given in mass percent and relate to the respectivecomplete mixture, all temperatures are given in degrees centigrade(Celsius) and all differences of temperatures in degrees centigrade. Allphysical properties have been and are determined according to “MerckLiquid Crystals, Physical Properties of Liquid Crystals”, StatusNovember 1997, Merck KGaA, Germany and are given for a temperature of20° C., unless explicitly stated otherwise. The optical anisotropy (Δn)is determined at a wavelength of 589.3 nm. The dielectric anisotropy(Δε) is determined at a frequency of 1 kHz. The threshold voltages, aswell as all other electro-optical properties have been determined withtest cells prepared at Merck KGaA, Germany. The test cells for thedetermination of Δε had a cell gap of 22 μm. The electrode was acircular ITO electrode with an area of 1.13 cm² and a guard ring. Theorientation layers were lecithin for homeotropic orientation (ε∥) andpolyimide AL-1054 from Japan Synthetic Rubber for homogeneuousorientation (ε⊥). The capacities were determined with a frequencyresponse analyser Solatron 1260 using a sine wave with a voltage of 0.3V_(rms). The light used in the electro-optical measurements was whitelight. The set up used was a commercially available equipment of Otsuka,Japan. The characteristic voltages have been determined underperpendicular observation. The threshold (V₁₀)-mid grey (V₅₀)- andsaturation (V₉₀) voltages have been determined for 10%, 50% and 90%relative contrast, respectively.

The liquid crystal media according to the present invention may containfurther additives and chiral dopants. It is especially preferred thatthey contain chiral dopants. The total concentration of these furtherconstituents is in the range of 0% to 20%, preferably 0.1% to 15%, morepreferably 1 to 15%, especially 1 to 6%, based in the total mixture. Theconcentrations of the individual compounds used each are preferably inthe range of 0.1 to 3%. The concentration of these and of similaradditives is not taken into consideration for the values and ranges ofthe concentrations of the liquid crystal components and compounds of theliquid crystal media in this application.

The inventive liquid crystal media according to the present inventionconsist of several compounds, preferably of 3 to 30, more preferably of5 to 20 and most preferably of 6 to 14 compounds. These compounds aremixed in conventional way. As a rule, the required amount of thecompound used in the smaller amount is dissolved in the compound used inthe greater amount. In case the temperature is above the clearing pointof the compound used in the higher concentration, it is particularlyeasy to observe completion of the process of dissolution. It is,however, also possible to prepare the media by other conventional ways,e.g. using so called pre-mixtures, which can be e.g. homologous oreutectic mixtures of compounds or using so called multi-bottle-systems,the constituents of which are ready to use mixtures themselves.

By addition of suitable additives, the liquid crystal media according tothe instant invention can be modified in such a way, that they areusable in all known types of liquid crystal displays, either using theliquid crystal media as such, like TN-, TN-AMD, ECB-, VAN-AMD and inparticular in composite systems, like PDLC-, NCAP- and PN-LCDs andespecially in HPDLCs. The LC media of the present invention areespecially suitable for use in light modulation elements and displaysusing a modulation (or controlling) medium which is in an opticallyisotropic state, preferably in the blue phase.

The melting point T(C,N) or T(C;I), the transition from the smectic (S)to the nematic (N) phase T(S,N) and the clearing point T(N,I) of theliquid crystals are given in degrees centigrade.

In the present application and especially in the following examples, thestructures of the liquid crystal compounds are represented byabbreviations also called acronyms. The transformation of theabbreviations into the corresponding structures is straight forwardaccording to the following two tables A and B. All groups C_(n)H_(2n+1)and C_(m)H_(2m+1) are straight chain alkyl groups with n respectively mC-atoms. The interpretation of table B is self-evident. Table A onlylists the abbreviations for the cores of the structures. The individualcompounds are denoted by the abbreviation of the core followed by ahyphen and a code specifying the substituents R¹, R², L¹ and L² follows:Code for R¹, R², L¹, L² R¹ R² L¹ L² nm C_(n)H_(2n+1) C_(m)H_(2m+1) H HnOm C_(n)H_(2n+1) OC_(m)H_(2m+1) H H nO.m OC_(n)H_(2n+1) C_(m)H_(2m+1) HH n C_(n)H_(2n+1) CN H H nN.F C_(n)H_(2n+1) CN H F nN.F.F C_(n)H_(2n+1)CN F F nF C_(n)H_(2n+1) F H H nF.F C_(n)H_(2n+1) F H F nF.F.FC_(n)H_(2n+1) F F F nOF OC_(n)H_(2n+1) F H H nCl C_(n)H_(2n+1) Cl H HnCl.F C_(n)H_(2n+1) Cl H F nCl.F.F C_(n)H_(2n+1) Cl F F nCF₃C_(n)H_(2n+1) CF₃ H H nOCF₃ C_(n)H_(2n+1) OCF₃ H H nOCF₃.F C_(n)H_(2n+1)OCF₃ H F nOCF₃.F.F C_(n)H_(2n+1) OCF₃ F F nOCF₂ C_(n)H_(2n+1) OCHF₂ H HnOCF₂.F C_(n)H_(2n+1) OCHF₂ H F nOCF₂.F.F C_(n)H_(2n+1) OCHF₂ F F nSC_(n)H_(2n+1) NCS H H nS.F C_(n)H_(2n+1) NCS H F nS.F.F C_(n)H_(2n+1)NCS F F rVsN C_(r)H_(2r+1)—CH═CH—C_(s)H_(2s)— CN H H rEsNC_(r)H_(2r+1)—O—C_(s)H_(2s)— CN H H nAm C_(n)H_(2n+1) COOC_(m)H_(2m+1) HH nF.Cl C_(n)H_(2n+1) Cl H F

TABLE A

PYP

PYRP

BCH

D

CPTP

EPCH

CEPTP

HP

ME

PCH

PDX

BECH

PTP

EBCH

ME

EHP

CQP

PUQP

CCQP

ET

TABLE B

PTP-n(O)mFF

CPTP-n(O)mFF

CGP-n.FX CGP-n.FX (X = F, CF3, OCHF2 or OCF3) (X = F, CF3, OCHF2 orOCF3)

CGU-n-X B-nO.FN (X = F, CF3, OCHF2 or OCF3)

Inm CB15

C15

CBC-nm

CBC-nmF

ECBC-nm

CHE CP-V-N

CP-nV-N

CPP-nV2-m

CPP-V-m

CPP-nV-m

CPP-V2-m G3.n

K3.n M3.n

PG-n-AN PU-n-AN

MU-n-AN PPYRP-nN

PPYP-nN PGP-n-N

PGIP-n-N PVG-n-S

PVG-nO-S PVG-V-S

PVG-nV-S PVG-Vn-S

PPVU-n-S

CPVP-n-N PTP-n(0)-S

PTG-n(0)-S PTU-n(0)-S

PTP-n(0)-N PTG-n(0)-N

PTU-n(0)-N

PTPG-n(0)-N GGP-n-CL

PGIGI-n-CL CGU-n-F

PPU-n-S PGU-n-S

PPU-n-F PGU-n-F

PPU-n-T PGU-n-T

BB3.n

PPTUI-n-m

GZU-nA-N GZU-nO-N

UZU-nA-N CUZU-n-F

CUZU-n-T CUZU-n-N

PUZU-n-F PUZU-n-T

PUZU-n-N AUZU-n-F

AUZU-n-T AUZU-n-N

AUUQP-n-F

AUUQP-n-T

AUUQP-n-OT

AUUQP-n-N

AUUQU-n-F

AUUQU-n-T

AUUQU-n-OT

AUUQU-n-N

AUUQGU-n-F

CUZP-n-SF5

PUZP-n-SF5

AUZP-n-SF5

AUUQP-n-SF5

P(Om)₂PQP-nO-F

P(Om)₂PQG-nO-F

P(Om)₂PQU-nO-F

P(Om)₂GQP-nO-F

P(Om)₂GQG-nO-F

P(Om)₂GQU-nO-F

P(Om)₂UQP-nO-F

P(Om)₂UQG-nO-F

P(Om)₂UQU-nO-F

P(Om)₂PQP-nO-T

P(Om)₂PQG-nO-T

P(Om)₂PQU-nO-T

P(Om)₂GQP-nO-T

P(Om)₂GQG-nO-T

P(Om)₂GQU-nO-T

P(Om)₂UQP-nO-T

P(Om)₂UQG-nO-T

P(Om)₂UQU-nO-T

P(Om)₂PQP-nO-OT

P(Om)₂PQG-nO-OT

P(Om)₂PQU-nO-OT

P(Om)₂GQP-nO-OT

P(Om)₂GQG-nO-OT

P(Om)₂GQU-nO-OT

P(Om)₂UQP-nO-OT

P(Om)₂UQG-nO-OT

P(Om)₂UQU-nO-OT

P(Om)₂PQPU-nO-SF5

P(Om)₂PQU-nO-SF5

P(Om)₂UQU-nO-SF5

P(Om)₂UQU-nO-SF5

P(Om)₂UQG(T)-nO-T

P(Om)₂UQP(T)₂-nO-T

P(On)₂UQU-nO-OT B(OC)2C*H-C-n z.B:

B(OC)2C*H-C-3 bzw, R-5011/S-5011 BO2C*H-n BO2C*F-n

BO2C*H-C-n BO2C*F-C-n

BO2C*H-CC-n BO2C*F-CC-n

(nOPZ)2X*

(n0PZPZ)2X*

SS-(nCPZ)2BE

RR-(nCPZ)2BE

C 15 CB 15

CM 21 R/S-811

CM 44 CM 45

CM 47

CN

R/S-2011

R/S-1011

R/S-3011

R/S-4011 R-5011/S-5011

The liquid crystal media according to the instant invention do containpreferably

-   -   four or more compounds selected from the group of compounds of        tables A and B and/or    -   five or more compounds selected from the group of compounds of        table B and/or    -   two or more compounds selected from the group of compounds of        table A.

EXAMPLES

The examples given in the following are illustrating the presentinvention without limiting it in any way.

However, the physical data especially of the compounds illustrate to theexpert which properties can be achieved in which ranges. Especially thecombination of the various properties, which can be preferably achieved,is thus well defined.

Example 11-[2,6-difluoro-(4-(2,4,6-tri-n-propoxyphenyl)phenyl)difluoromethoxy]-3,4,5-trifluorobenzene

is prepared according to Scheme I. It has a melting point of 70° C., amelting enthalpy of 6.8 kcal/mol and a glass transition temperature of−27° C. It is melting from the crystalline phase into the isotropicphase.

Example 2

Analogously to example 1 the corresponding compound with threen-butyloxy groups1-[2,6-difluoro-(4-(2,4,6-tri-n-butoxyphenyl)phenyl)-difluoromethoxy]-3,4,5-trifluorobenzene

is prepared. It has a melting point of 51° C., a melting enthalpy of 7.9kcal/mol and, like the compound of example 1, is melting from thecrystalline phase to the isotropic phase.

Example 3 Analogously to example 1 the corresponding compound with threen-hexyloxy groups1-[2,6-difluoro-(4-(2,4,6-tri-n-hexoxyphenyl)phenyl)-difluoromethoxy]-3,4,5-trifluorobenzene

is prepared. It has a melting point of −53° C. and is melting from theglass phase to the isotropic phase.

Examples 4 to 45

Analogously to Example 1 the following compounds are prepared:

No. R¹¹ to R¹³ Y¹¹ Y¹² Phases (T/° C.) 4 CH₃ H H 5 C₂H₅ H H 6 n-C₃H₇ H H7 n-C₄H₉ H H 8 n-C₅H₁₁ H H 9 n-C₆H₁₃ H H 10 n-C₇H₁₅ H H 11 n-C₈H₁₇ H H12 n-C₉H₁₉ H H 13 CH₂═CH H H 14 CH₂═CH—CH₂ H H 15 E-CH₃—CH₂═CH H H 16CH₂═CH—(CH₂)₂ H H 17 E-CH₃—CH₂═CH—CH₂ H H 18 E-CH₃—CH₂—CH₂═CH H H 19 CH₃F H 20 C₂H₅ F H 21 n-C₃H₇ F H 22 n-C₄H₉ F H 23 n-C₅H₁₁ F H 24 n-C₆H₁₃ FH 25 n-C₇H₁₅ F H 26 n-C₈H₁₇ F H 27 n-C₉H₁₉ F H 28 CH₂═CH F H 29CH₂═CH—CH₂ F H 30 E-CH₃—CH₂═CH F H 31 CH₂═CH—(CH₂)₂ F H 32E-CH₃—CH₂═CH—CH₂ F H 33 E-CH₃—CH₂—CH₂═CH F H 34 CH₃ F F 35 C₂H₅ F F C.76° C. I, T_(g) = −14° C. 1 n-C₃H₇ F F C. 70° C. I, T_(g) = −53° C. 2n-C₄H₉ F F C. 51° C. I 36 n-C₅H₁₁ F F T_(g) = −52° C. 3 n-C₆H₁₃ F FT_(g) = −53° C. 37 n-C₇H₁₅ F F T_(g) = −62° C. 38 n-C₈H₁₇ F F T_(g) =−59° C. 39 n-C₉H₁₉ F F 40 CH₂═CH F F 41 CH₂═CH—CH₂ F F 42 E-CH₃—CH₂═CH FF 43 CH₂═CH—(CH₂)₂ F F 44 E-CH₃—CH₂═CH—CH₂ F F 45 E-CH₃—CH₂—CH₂═CH F F

Example 461-[2,6-difluoro-(4-(2,4,6-tri-n-propoxyphenyl)phenyl)difluoromethoxy]-4-trifluoromethylbenzene

is prepared analogously to example 1. The compound has a melting pointof 66° C. and a melting enthalpy of 7.5 kcal/mol. It is melting from thecrystalline glass phase into the isotropic phase.

Example 471-[2,6-difluoro-(4-(2,4,6-tri-n-propoxyphenyl)phenyl)difluoromethoxy]-3,5-difluoro-4-trifluoromethylbenzene

is prepared analogously to example 1. The compound has a glasstransition temperature of −23° C., a melting point of 50° C. and amelting enthalpy of 6.8 kcal/mol. It is melting from the glass phaseinto the isotropic phase.

Examples 48 to 90

Analogously to Example 47 the following compounds are prepared:

No. R¹¹ to R¹³ Y¹¹ Y¹² Phases (T/° C.) 48 CH₃ H H 49 C₂H₅ H H 46 n-C₃H₇H H C. 66° C. I 50 n-C₄H₉ H H 51 n-C₅H₁₁ H H 52 n-C₆H₁₃ H H 53 n-C₇H₁₅ HH 54 n-C₈H₁₇ H H 55 n-C₉H₁₉ H H 56 CH₂═CH H H 57 CH₂═CH—CH₂ H H 58E-CH₃—CH₂═CH H H 59 CH₂═CH—(CH₂)₂ H H 60 E-CH₃—CH₂═CH—CH₂ H H 61E-CH₃—CH₂—CH₂═CH H H 62 CH₃ F H 63 C₂H₅ F H 64 n-C₃H₇ F H 65 n-C₄H₉ F H66 n-C₅H₁₁ F H 67 n-C₆H₁₃ F H 68 n-C₇H₁₅ F H 69 n-C₈H₁₇ F H 70 n-C₉H₁₉ FH 71 CH₂═CH F H 72 CH₂═CH—CH₂ F H 73 E-CH₃—CH₂═CH F H 74 CH₂═CH—(CH₂)₂ FH 75 E-CH₃—CH₂═CH—CH₂ F H 76 E-CH₃—CH₂—CH₂═CH F H 77 CH₃ F F 78 C₂H₅ F F47 n-C₃H₇ F F T_(g) = −23° C., C. 50° C. I 79 n-C₄H₉ F F 80 n-C₅H₁₁ F F81 n-C₆H₁₃ F F T_(g) = −50° C., C. ° C. I 82 n-C₇H₁₅ F F 83 n-C₈H₁₇ F F84 n-C₉H₁₉ F F 85 CH₂═CH F F 86 CH₂═CH—CH₂ F F 87 E-CH₃—CH₂═CH F F 88CH₂═CH—(CH₂)₂ F F 89 E-CH₃—CH₂═CH—CH₂ F F 90 E-CH₃—CH₂—CH₂═CH F F

Examples 91 to 135

Analogously to Example 47 the following compounds are prepared:

No. R¹¹ to R¹³ Y¹¹ Y¹² Phases (T/° C.) 91 CH₃ H H 92 C₂H₅ H H 93 n-C₃H₇H H 94 n-C₄H₉ H H 95 n-C₅H₁₁ H H 96 n-C₆H₁₃ H H 97 n-C₇H₁₅ H H 98n-C₈H₁₇ H H 99 n-C₉H₁₉ H. H 100 CH₂═CH H H 101 CH₂═CH—CH₂ H H 102E-CH₃—CH₂═CH H H 103 CH₂═CH—(CH₂)₂ H H 104 E-CH₃—CH₂═CH—CH₂ H H 105E-CH₃—CH₂—CH₂═CH H H 106 CH₃ F H 107 C₂H₅ F H 108 n-C₃H₇ F H 109 n-C₄H₉F H 110 n-C₅H₁₁ F H 111 n-C₆H₁₃ F H 112 n-C₇H₁₅ F H 113 n-C₈H₁₇ F H 114n-C₉H₁₉ F H 115 CH₂═CH F H 116 CH₂═CH—CH₂ F H 117 E-CH₃—CH₂═CH F H 118CH₂═CH—(CH₂)₂ F H 119 E-CH₃—CH₂═CH—CH₂ F H 120 E-CH₃—CH₂—CH₂═CH F H 121CH₃ F F 122 C₂H₅ F F 123 n-C₃H₇ F F 124 n-C₄H₉ F F 125 n-C₅H₁₁ F F 126n-C₆H₁₃ F F 127 n-C₇H₁₅ F F 128 n-C₈H₁₇ F F 129 n-C₉H₁₉ F F 130 CH₂═CH FF 131 CH₂═CH—CH₂ F F 132 E-CH₃—CH₂═CH F F 133 CH₂═CH—(CH₂)₂ F F 134E-CH₃—CH₂═CH—CH₂ F F 135 E-CH₃—CH₂—CH₂═CH F F

Example 136

Analogously to example 1

is prepared. The compound has a glass transition temperature of −31° C.It is melting from the glass phase into the isotropic phase.

Example 137 Analogously to example11-[2,6-difluoro-(4-(2,4,6-tri-n-docecoxyphenyl)-phenyl)difluoromethoxy]-3,4,5-trifluorobenzene

is prepared. The compound has a melting point of 16° C., a meltingenthalpy of 11.0 kcal/mol and an enthalpy of crystallisation of 3.7kcal/mol.

It is melting from the crystalline phase into the isotropic phase.

Example 138 Analogously to example11-[2,6-difluoro-(4-(2,4,6-tri-n-propxyphenyl)-phenyl)difluoromethoxy]-3,5-difluoro-4-cyano-benzene

is prepared. The compound has a glass transition temperature of −14° C.and a melting point of 89° C. It is melting from the glass phase intothe isotropic phase.

Example 139 to 168

Analogously to Example 1 the following compounds are prepared:

No. R¹¹ to R¹³ Y¹¹ Phases (T/° C.) 139 CH₃ H 140 C₂H₅ H 141 n-C₃H₇ H 142n-C₄H₉ H 143 n-C₅H₁₁ H 144 n-C₆H₁₃ H 145 n-C₇H₁₅ H 146 n-C₈H₁₇ H 147n-C₉H₁₉ H 148 CH₂═CH H 149 CH₂═CH—CH₂ H 150 E-CH₃—CH₂═CH H 151CH₂═CH—(CH₂)₂ H 152 E-CH₃—CH₂═CH—CH₂ H 153 E-CH₃—CH₂—CH₂═CH H 154 CH₃ F155 C₂H₅ F 156 n-C₃H₇ F 157 n-C₄H₉ F 158 n-C₅H₁₁ F 159 n-C₆H₁₃ F 160n-C₇H₁₅ F 161 n-C₈H₁₇ F 162 n-C₉H₁₉ F 163 CH₂═CH F 164 CH₂═CH—CH₂ F 165E-CH₃—CH₂═CH F 166 CH₂═CH—(CH₂)₂ F 167 E-CH₃—CH₂═CH—CH₂ F 168E-CH₃—CH₂—CH₂═CH F

Example 169 to 258

Analogously to Example 1 the following compounds are prepared:

No. R¹¹ to R¹³ Y¹¹ Y¹² Phases (T/° C.) 169 CH₃ H H 170 C₂H₅ H H 171n-C₃H₇ H H C. 76° C. I 172 n-C₄H₉ H H 173 n-C₅H₁₁ H H 174 n-C₆H₁₃ H H175 n-C₇H₁₅ H H 176 n-C₈H₁₇ H H 177 n-C₉H₁₉ H H 178 CH₂═CH H H 179CH₂═CH—CH₂ H H 180 E-CH₃—CH₂═CH H H 181 CH₂═CH—(CH₂)₂ H H 182E-CH₃—CH₂═CH—CH₂ H H 183 E-CH₃—CH₂—CH₂═CH H H 184 CH₃ F H 185 C₂H₅ F H186 n-C₃H₇ F H 187 n-C₄H₉ F H 188 n-C₅H₁₁ F H 189 n-C₆H₁₃ F H 190n-C₇H₁₅ F H 191 n-C₈H₁₇ F H 192 n-C₉H₁₉ F H 193 CH₂═CH F H 194CH₂═CH—CH₂ F H 195 E-CH₃—CH₂═CH F H 196 CH₂═CH—(CH₂)₂ F H 197E-CH₃—CH₂═CH—CH₂ F H 198 E-CH₃—CH₂—CH₂═CH F H 199 CH₃ CF₃ H 200 C₂H₅ CF₃H 201 n-C₃H₇ CF₃ H 202 n-C₄H₉ CF₃ H 203 n-C₅H₁₁ CF₃ H 204 n-C₆H₁₃ CF₃ H205 n-C₇H₁₅ CF₃ H 206 n-C₈H₁₇ CF₃ H 207 n-C₉H₁₉ CF₃ H 208 CH₂═CH CF₃ H209 CH₂═CH—CH₂ CF₃ H 210 E-CH₃—CH₂═CH CF₃ H 211 CH₂═CH—(CH₂)₂ CF₃ H 212E-CH₃—CH₂═CH—CH₂ CF₃ H 213 E-CH₃—CH₂—CH₂═CH CF₃ H 214 CH₃ F F 215 C₂H₅ FF 216 n-C₃H₇ F F 217 n-C₄H₉ F F 218 n-C₅H₁₁ F F 219 n-C₆H₁₃ F F 220n-C₇H₁₅ F F 221 n-C₈H₁₇ F F 222 n-C₉H₁₉ F F 223 CH₂═CH F F 224CH₂═CH—CH₂ F F 225 E-CH₃—CH₂═CH F F 226 CH₂═CH—(CH₂)₂ F F 227E-CH₃—CH₂═CH—CH₂ F F 228 E-CH₃—CH₂—CH₂═CH F F 229 CH₃ CF₃ F 230 C₂H₅ CF₃F 231 n-C₃H₇ CF₃ F 232 n-C₄H₉ CF₃ F 233 n-C₅H₁₁ CF₃ F 234 n-C₆H₁₃ CF₃ F235 n-C₇H₁₅ CF₃ F 236 n-C₈H₁₇ CF₃ F 237 n-C₉H₁₉ CF₃ F 238 CH₂═CH CF₃ F239 CH₂═CH—CH₂ CF₃ F 240 E-CH₃—CH₂═CH CF₃ F 241 CH₂═CH—(CH₂)₂ CF₃ F 242E-CH₃—CH₂═CH—CH₂ CF₃ F 243 E-CH₃—CH₂—CH₂═CH CF₃ F 244 CH₃ CF₃ CF₃ 245C₂H₅ CF₃ CF₃ 246 n-C₃H₇ CF₃ CF₃ 247 n-C₄H₉ CF₃ CF₃ 248 n-C₅H₁₁ CF₃ CF₃249 n-C₆H₁₃ CF₃ CF₃ 250 n-C₇H₁₅ CF₃ CF₃ 251 n-C₈H₁₇ CF₃ CF₃ 252 n-C₉H₁₉CF₃ CF₃ 253 CH₂═CH CF₃ CF₃ 254 CH₂═CH—CH₂ CF₃ CF₃ 255 E-CH₃—CH₂═CH CF₃CF₃ 256 CH₂═CH—(CH₂)₂ CF₃ CF₃ 257 E-CH₃—CH₂═CH—CH₂ CF₃ CF₃ 258E-CH₃—CH₂—CH₂═CH CF₃ CF₃

Example 259 to 348

Analogously to Example 1 the following compounds are prepared:

No. R¹¹ to R¹³ Y¹¹ Y¹² Phases (T/° C.) 259 CH₃ H H 260 C₂H₅ H H 261n-C₃H₇ H H T_(g) −5° C. C. 79° C. I 262 n-C₄H₉ H H 263 n-C₅H₁₁ H H 264n-C₆H₁₃ H H 265 n-C₇H₁₅ H H 266 n-C₈H₁₇ H H 267 n-C₉H₁₉ H H 268 CH₂═CH HH 269 CH₂═CH—CH₂ H H 270 E-CH₃—CH₂═CH H H 271 CH₂═CH—(CH₂)₂ H H 272E-CH₃—CH₂═CH—CH₂ H H 273 E-CH₃—CH₂—CH₂═CH H H 274 CH₃ F H 275 C₂H₅ F H276 n-C₃H₇ F H 277 n-C₄H₉ F H 278 n-C₅H₁₁ F H 279 n-C₆H₁₃ F H 280n-C₇H₁₅ F H 281 n-C₈H₁₇ F H 282 n-C₉H₁₉ F H 283 CH₂═CH F H 284CH₂═CH—CH₂ F H 285 E-CH₃—CH₂═CH F H 286 CH₂═CH—(CH₂)₂ F H 287E-CH₃—CH₂═CH—CH₂ F H 288 E-CH₃—CH₂—CH₂═CH F H 289 CH₃ CF₃ H 290 C₂H₅ CF₃H 291 n-C₃H₇ CF₃ H 292 n-C₄H₉ CF₃ H 293 n-C₅H₁₁ CF₃ H 294 n-C₆H₁₃ CF₃ H295 n-C₇H₁₅ CF₃ H 296 n-C₈H₁₇ CF₃ H 297 n-C₉H₁₉ CF₃ H 298 CH₂═CH CF₃ H299 CH₂═CH—CH₂ CF₃ H 300 E-CH₃—CH₂═CH CF₃ H 301 CH₂═CH—(CH₂)₂ CF₃ H 302E-CH₃—CH₂═CH—CH₂ CF₃ H 303 E-CH₃—CH₂—CH₂═CH CF₃ H 304 CH₃ F F 305 C₂H₅ FF 306 n-C₃H₇ F F T_(g) −22° C. I 307 n-C₄H₉ F F 308 n-C₅H₁₁ F F 309n-C₆H₁₃ F F 310 n-C₇H₁₅ F F 311 n-C₈H₁₇ F F 312 n-C₉H₁₉ F F 313 CH₂═CH FF 314 CH₂═CH—CH₂ F F 315 E-CH₃—CH₂═CH F F 316 CH₂═CH—(CH₂)₂ F F 317E-CH₃—CH₂═CH—CH₂ F F 318 E-CH₃—CH₂—CH₂═CH F F 319 CH₃ CF₃ F 320 C₂H₅ CF₃F 321 n-C₃H₇ CF₃ F 322 n-C₄H₉ CF₃ F 323 n-C₅H₁₁ CF₃ F 324 n-C₆H₁₃ CF₃ F325 n-C₇H₁₅ CF₃ F 326 n-C₈H₁₇ CF₃ F 327 n-C₉H₁₉ CF₃ F 328 CH₂═CH CF₃ F329 CH₂═CH—CH₂ CF₃ F 330 E-CH₃—CH₂═CH CF₃ F 331 CH₂═CH—(CH₂)₂ CF₃ F 332E-CH₃—CH₂═CH—CH₂ CF₃ F 333 E-CH₃—CH₂—CH₂═CH CF₃ F 334 CH₃ CF₃ CF₃ 335C₂H₅ CF₃ CF₃ 336 n-C₃H₇ CF₃ CF₃ 337 n-C₄H₉ CF₃ CF₃ 338 n-C₅H₁₁ CF₃ CF₃339 n-C₆H₁₃ CF₃ CF₃ 340 n-C₇H₁₅ CF₃ CF₃ 341 n-C₈H₁₇ CF₃ CF₃ 342 n-C₉H₁₉CF₃ CF₃ 343 CH₂═CH CF₃ CF₃ 344 CH₂═CH—CH₂ CF₃ CF₃ 345 E-CH₃—CH₂═CH CF₃CF₃ 346 CH₂═CH—(CH₂)₂ CF₃ CF₃ 347 E-CH₃—CH₂═CH—CH₂ CF₃ CF₃ 348E-CH₃—CH₂—CH₂═CH CF₃ CF₃

Example 349 to 393

Analogously to Example 1 the following compounds are prepared:

No. R¹¹ to R¹³ Y¹¹ Y¹² Phases (T/° C.) 349 CH₃ CF₃ H 350 C₂H₅ CF₃ H 351n-C₃H₇ CF₃ H 352 n-C₄H₉ CF₃ H 353 n-C₅H₁₁ CF₃ H 354 n-C₆H₁₃ CF₃ H 355n-C₇H₁₅ CF₃ H 356 n-C₈H₁₇ CF₃ H 357 n-C₉H₁₉ CF₃ H 358 CH₂═CH CF₃ H 359CH₂═CH—CH₂ CF₃ H 360 E-CH₃—CH₂═CH CF₃ H 361 CH₂═CH—(CH₂)₂ CF₃ H 362E-CH₃—CH₂═CH—CH₂ CF₃ H 363 E-CH₃—CH₂—CH₂═CH CF₃ H 364 CH₃ CF₃ F 365 C₂H₅CF₃ F 366 n-C₃H₇ CF₃ F 367 n-C₄H₉ CF₃ F 368 n-C₅H₁₁ CF₃ F 369 n-C₆H₁₃CF₃ F 370 n-C₇H₁₅ CF₃ F 371 n-C₈H₁₇ CF₃ F 372 n-C₉H₁₉ CF₃ F 373 CH₂═CHCF₃ F 374 CH₂═CH—CH₂ CF₃ F 375 E-CH₃—CH₂═CH CF₃ F 376 CH₂═CH—(CH₂)₂ CF₃F 377 E-CH₃—CH₂═CH—CH₂ CF₃ F 378 E-CH₃—CH₂—CH₂═CH CF₃ F 379 CH₃ CF₃ CF₃380 C₂H₅ CF₃ CF₃ 381 n-C₃H₇ CF₃ CF₃ 382 n-C₄H₉ CF₃ CF₃ 383 n-C₅H₁₁ CF₃CF₃ 384 n-C₆H₁₃ CF₃ CF₃ 385 n-C₇H₁₅ CF₃ CF₃ 386 n-C₈H₁₇ CF₃ CF₃ 387n-C₉H₁₉ CF₃ CF₃ 388 CH₂═CH CF₃ CF₃ 389 CH₂═CH—CH₂ CF₃ CF₃ 390E-CH₃—CH₂═CH CF₃ CF₃ 391 CH₂═CH—(CH₂)₂ CF₃ CF₃ 392 E-CH₃—CH₂═CH—CH₂ CF₃CF₃ 393 E-CH₃—CH₂—CH₂═CH CF₃ CF₃

Examples 394 to 471

Analogously to example 1 the following compounds were prepared: Ex. #Structure of Compound Properties 394

M.P. = 79° C.; 395

Tg = 12° C., M.P. = 76° C.; 396

M.P. = 114° C.; 397

Tg = −11° C., M.P. = 78° C.; 398

Tg = 6° C., M.P. = 73° C.; 399

Tg = −9° C., M.P. = 81° C.; 400

M.P. = 53° C., Δn = −0.082, Δε = 7.3, 401

Tg = −3° C., M.P. = 109° C.; 402

M.P. = 111° C., Δn = 0.045, Δε = 14.4; 403

M.P. = 40° C.; 404

Tg = −5° C., M.P. = 74° C.; 405

M.P. = 54° C.; 406

M.P. = 98° C.; 407

Tg = −17° C., M.P. = 69° C.; 408

Tg = −25° C., M.P. = 63° C., 409

Δn = 0.006, Δε = 12.4, Tg = −53° C.; 410

M.P. = 34° C.; 411

Δn = −0.026, Δε = 15.2, Tg = −30° C.; 412

413

Tg = −58° C.; 414

Δn = −0.033, Δε = 2.9; 415

Tg = −65° C., M.P. = 31° C.; 416

Tg = −35° C., M.P. = 65° C.; 417

M.P. = 83° C.; 418

419

420

Δn = 0.057, Δε = 12.9, Tg = −37, M.P. = 43° C.; 421

Δn = 0.135, Δε = 32.4; 422

Δn = 0.057, Δε = 16.7, Tg = −31, M.P. = 47° C.; 423

Δn = 0.103, Δε = 15.2, Tg = −18, M.P. = 65° C.; 424

Δn = 0.074, Δε = 21.3, M.P. = −7° C.; 425

M.P. = 94° C.; 426

M.P. = 82° C.; 427

Tg = −5° C., M.P. = 87° C.; 428

Tg = −11° C.; 429

430

431

HTP = +3.5 μm⁻¹, Tg = −61° C.; 432

HTP = +3.4 μm⁻¹, Tg = −54° C.; 433

Tg = −19° C., M.P. = 78° C.; 434

Δn = 0.047, Δε = 27.5, M.P. = 79° C.; 435

Δn = 0.046, Δε = 21.3, M.P. = 63° C.; 436

Tg = −16° C., M.P. = 67° C.; 437

Δn = 0.034, Δε = 19.0, Tg = −15° C., M.P. = 87° C.; 438

M.P. = 124° C.; 439

Tg = −1° C., M.P. = 120° C.; 440

Δn = −0.024, Δε = 14.7; 441

Δn = 0.032, Δε = 26.1; 442

Tg = −26° C., M.P. = 64° C.; 443

Tg = −33° C., M.P. = 69° C.; 444

HTP = −22.8 μm⁻¹M.P. = 95° C.; 445

HTP = +22.7 μm⁻¹M.P. = 95° C.; 446

447

448

449

M.P. = 137; 450

Δn = 0.039, Δε = 11.8, M.P. = 76° C.; 451

Δn = 0.086, Δε = 14.9, M.P. = 72° C.; 452

Δn = 0.037, Δε = 17.1; 453

Δn = 0.081, Δε = 21.3, M.P. = 74° C.; 454

455

Δn = 0.079, Δε = 31.8, Tg = −24° C., M.P. = 69° C.; 456

M.P. = 123° C.; 457

458

M.P. = 62° C.; 459

Δn = 0.000, Δε = 3.0, Tg = −51° C.; 460

Δn = 0.049, Δε = 6.0, Tg = −36° C., M.P. = 44° C.; 461

Δn = 0.121, Δε = 9.3, Tg = −23° C., T(K,S_(x)) = 90° C., M.P. = (−5)°C.; 462

Δn = 0.046, Δε = 4.9, Tg = −35° C.; 463

Δn = 0.168, Δε = 9.3, Tg = −9° C., T(K,N) = 104° C., T(N,I) = 41.9° C.;464

Δn = 0.090, Δε = 6.6, Tg = −319 C., M.P. = 67° C.; 465

Δn = −050, Δε = 10.8; 466

Tg = −15° C.; 467

M.P. = 34° C.; 468

Δn = 0.137, Δε = 15.2; M.P. = 120° C.; 469

Δn = 0.074, Δε = 21.3, M.P. = −7° C.; 470

Δn = 0.074, Δε = 13.2, Tg = −27° C. M.P. = 54° C. 471

Tg = −36° C., M.P. = 39° C.;Remarks: Δn and Δε extrapolated from 10% solution in ZLI-4792 and HTP inMLC-6260, both mixtures from Merck KGaA, all data except transitiontemperatures given at 20° C.

USE-EXAMPLES Use-Example 1

A liquid crystal mixture, host mixture A, is realised consisting of:Mixture A Compound Concentration/ Abbreviation mass-% GZU-3A-N 15.0GZU-4A-N 15.0 GZU-4O-N 15.0 UZU-3A-N 8.0 CUZU-2-N 9.0 CUZU-3-N 9.0CUZU-4-N 9.0 HP-3N.F 6.0 HP-4N.F 6.0 HP-5N.F 8.0 Σ 100.0

This mixture has the following properties:

Clearing point (T(N,I))/° C.: 56.8

To 85.0% of this mixture 5% of the chiral dopant R-5011 and 10% of thecompound of interest are added and the properties of the resultingmixture are determined.

The data are compiled in table 1.

T_(g), T (K,I) and T(g,I) given in Tables 1a, 1b below are determined bymeans of DSC (differential scanning calorimetry) and microscopy.

Further electro-optical data given in the tables below are measured in atest cell as described hereinafter: This test cell is an electro-opticalcell with interdigital electrodes having a distance of electrodes of 10μm, a width of electrodes of 10 μm, and a cell thickness of 10 μm. Theheight of the electrodes—that are made out of chromium and without apolyimid layer—can be ignored in comparison to the cell thickness.Experimental values are determined by using the standard apparatus asused in DE 102 41 301.0.

T_(trans) is the characteristic temperature which is defined as follows:

-   -   If the characteristic voltage as a function of temperature has a        minimum, the temperature at this minimum is denoted as        characteristic temperature;    -   If the characteristic voltage as a function of temperature has        no minimum and if the controlling medium has one or more blue        phases, the transistion temperature to the blue phase is denoted        as characteristic temperature; in case there are more than one        blue phase, the lowest transition temperature to a blue phase is        denoted as characteristic temperature;    -   If the characteristic voltage as a function of temperature has        no minimum and if the controlling medium has no blue phase, the        transistion temperature to the isotropic phase is denoted as        characteristic temperature.

In this context the term “characteristic voltage” refers to a specificvoltage, e.g. the threshold voltage V₁₀ at which a light transmission of10% is observed or the saturation voltage V₉₀ at which a transmission of90% is observed.$\frac{\mathbb{d}V^{*}}{\mathbb{d}T}\text{:} = \frac{\frac{\mathbb{d}V}{\mathbb{d}T}\left( {T_{trans} + 2} \right)}{V\left( {T_{trans} + 2} \right)}$

In each case 10% of the respective compound of interest have beendissolved together with 5% of the chiral dopant R-5011 in the hostmixture A, both available from Merck KGaA, Germany.

The results are shown in the following tables (Tables 1a to 1w). TABLE1a Use example 1.1 1.2 1.3 1.4 Compound of example 1 2 3 47 T_(g)/° C. —— −53 −23 T(K, I)/° C. 69 51 48 T(g, I)/° C. — — −53 — T_(trans)./° C.−2 −2 1 1 T trans. − Iso/deg. 9 9 12 12 ΔT/deg. 11 11 11 11 V₁₀₀(Ttrans. + 2)/V 43 39 36 33 dV/dT(T trans. + 2)/V/deg. 1.0 1.0 1.0 1.0dV*/dT(T trans. + 2)/deg.⁻¹ 0.02 0.03 0.03 0.03

TABLE 1b Use example 1.5 1.6 1.7 1.8 Compound of example 46 137 136 138T_(g)/° C. — — −31 −14 T(K, I)/° C. 66 16 — 89 T(g, I)/° C. — — — — Ttrans/° C. 1.0 10.5 11.0 6.0 T trans − Iso/deg. 13 19.5 n.d. 15.5ΔT/deg. 12 9 n.d. 9.5 V₁₀₀(T trans. + 2)/V 38 40 n.d. 36 dV/dT(Ttrans. + 2)/V/deg. 1.0 1.5 n.d. 1.5 dV*/dT(T trans. + 2)/deg.⁻¹ 0.030.03 n.d. 0.04

TABLE 1c Use example 1.9 1.10 1.11 1.12 Compound of example 35 36 37 38T_(trans)./° C. 7.5 2.5 4.6 6.2 T trans. − Iso/deg. 17.6 10.3 16.0 16.1ΔT/deg. 10.1 7.8 11.4 9.9 V₁₀₀(T trans. + 2)/V 35 35 34.5 40.5 dV/dT(Ttrans. + 2)/V/deg. 0.05 0 2.0 1.8 dV*/dT(T trans. + 2)/deg.⁻¹ 0.001 00.06 0.05

TABLE 1d Use example 1.13 1.14 1.15 1.16 Compound of example 171 261 306394 T_(trans)./° C. 0.0 n.d. 4.0 7.5 T trans. − Iso/deg. 12.0 n.d. 11.018.0 ΔT/deg. 12.0 n.d. 7.0 10.5 V₁₀₀(T trans. + 2)/V 36 n.d. 38 39.5dV/dT(T trans. + 2)/V/deg. 0 n.d. 1.0 4.5 dV*/dT(T trans. + 2)/deg.⁻¹ 0n.d. 0.03 0.12

TABLE 1e Use example 1.17 1.18 1.19 1.20 Compound of example 395 396 397398 T_(trans)./° C. 5.0 n.d. 5.0 n.d. T trans. − Iso/deg. 14.0 n.d. 15.5n.d. ΔT/deg. 9.0 n.d. 10.5 n.d. V₁₀₀(T trans. + 2)/V 37 n.d. 37 n.d.dV/dT(T trans. + 2)/V/deg. 1.0 n.d. 1.0 n.d. dV*/dT(T trans. + 2)/deg.⁻¹0.02 n.d. 0.03 n.d.Remarks:n.d.: not determined.

TABLE 1f Use example 1.21 1.22 1.23 1.24 Compound of example 399 400 401402 T_(trans)./° C. n.d. n.d. −5.6 −3.1 T trans. − Iso/deg. n.d. n.d.9.3 8.9 ΔT/deg. n.d. n.d. 14.8 12.0 V₁₀₀(T trans. + 2)/V n.d. n.d. 39 36dV/dT(T trans. + 2)/V/deg. n.d. n.d. 0 0 dV*/dT(T trans. + 2)/deg.⁻¹n.d. n.d. 0 0

TABLE 1g Use example 1.25 1.26 1.27 1.28 Compound of example 403 404 405406 T_(trans)./° C. −3.0 4.0 n.d. n.d. T trans. − Iso/deg. 12.0 16.5n.d. n.d. ΔT/deg. 15.0 12.5 n.d. n.d. V₁₀₀(T trans. + 2)/V 35 30 n.d.n.d. dV/dT(T trans. + 2)/V/deg. 1.0 1.0 n.d. n.d. dV*/dT(T trans. +2)/deg.⁻¹ 0.03 0.03 n.d. n.d.

TABLE 1h Use example 1.29 1.30 1.31 1.32 Compound of example 407 408 409410 T_(trans)./° C. n.d. −5.5 −3.0 −0.9 T trans. − Iso/deg. n.d. 8.512.0 11.4 ΔT/deg. n.d. 14.0 15.0 12.3 V₁₀₀(T trans. + 2)/V n.d. 37 3539.5 dV/dT(T trans. + 2)/V/deg. n.d. 0.5 1.0 1.15 dV*/dT(T trans. +2)/deg.⁻¹ n.d. 0.01 0.01 0.04Remarks:n.d.: not determined.

TABLE 1i Use example 1.33 1.34 1.35 1.36 Compound of example 411 412 413414 T_(trans)./° C. −0.8 n.d. 5.3 11.0 T trans. − Iso/deg. 12.5 n.d.17.5 13.5 ΔT/deg. 13.3 n.d. 12.2 2.5 V₁₀₀(T trans. + 2)/V 34 n.d. 36 140dV/dT(T trans. + 2)/V/deg. 1.3 n.d. 0 10 dV*/dT(T trans. + 2)/deg.⁻¹0.04 n.d. 0 0.08

TABLE 1j Use example 1.37 1.38 1.39 1.40 Compound of example 415 416 417418 T_(trans)./° C. 1.3 4.1 24.0 5.0 T trans. − Iso/deg. 12.8 15.3 30.516.5 ΔT/deg. 11.5 11.2 6.5 11.5 V₁₀₀(T trans. + 2)/V 37 35.5 36 42dV/dT(T trans. + 2)/V/deg. 1.1 2.0 2.0 1 dV*/dT(T trans. + 2)/deg.⁻¹0.03 0.05 0.06 0.02

TABLE 1k Use example 1.41 1.42 1.43 1.44 Compound of example 419 420 421422 T_(trans)./° C. 24.0 7.5 14.0 n.d. T trans. − Iso/deg. 30.5 18.723.1 n.d. ΔT/deg. 6.5 11.2 9.1 n.d. V₁₀₀(T trans. + 2)/V 36 37.5 32 n.d.dV/dT(T trans. + 2)/V/deg. 2.0 1.35 2.0 n.d. dV*/dT(T trans. + 2)/deg.⁻¹0.06 0.04 0.06 n.d.Remarks:n.d.: not determined.

TABLE 1l Use example 1.45 1.46 1.47 1.48 Compound of example 423 424 425426 T_(trans)./° C. 12.6 7.3 14.0 14.0 T trans. − Iso/deg. 21.9 19.422.5 22.0 ΔT/deg. 9.3 12.1 8.5 8.0 V₁₀₀(T trans. + 2)/V 39.5 43.5 36 36dV/dT(T trans. + 2)/V/deg. 2.3 0.7 2.0 2.0 dV*/dT(T trans. + 2)/deg.⁻¹0.04 0.02 0.06 0.06

TABLE 1m Use example 1.49 1.50 1.51 1.52 Compound of example 427 428 429430 T_(trans)./° C. n.d. 4.5 2.8 n.d. T trans. − Iso/deg. n.d. 16.0 12.0n.d. ΔT/deg. n.d. 11.5 9.2 n.d. V₁₀₀(T trans. + 2)/V n.d. 38 35.5 n.d.dV/dT(T trans. + 2)/V/deg. n.d. 1.0 1.1 n.d. dV*/dT(T trans. + 2)/deg.⁻¹n.d. 0.03 0.04 n.d.

TABLE 1n Use example 1.53 1.54 1.55 1.56 Compound of example 431 432 433434 T_(trans)./° C. n.d. 14.5 n.d. n.d. T trans. − Iso/deg. n.d. 20.7n.d. n.d. ΔT/deg. n.d. 6.2 n.d. n.d. V₁₀₀(T trans. + 2)/V n.d. 111.5n.d. n.d. dV/dT(T trans. + 2)/V/deg. n.d. 9.1 n.d. n.d. dV*/dT(Ttrans. + 2)/deg.⁻¹ n.d. 0.05 n.d. n.d.Remarks:n.d.: not determined.

TABLE 1o Use example 1.57 1.58 1.59 1.60 Compound of example 435 436 437438 T_(trans)./° C. n.d. 9.0 9.4 n.d. T trans. − Iso/deg. n.d. 19.3 19.5n.d. ΔT/deg. n.d. 9.3 10.1 n.d. V₁₀₀(T trans. + 2)/V n.d. 37 38 n.d.dV/dT(T trans. + 2)/V/deg. n.d. 2.5 1.1 n.d. dV*/dT(T trans. + 2)/deg.⁻¹n.d. 0.07 0.03 n.d.

TABLE 1p Use example 1.61 1.62 1.63 1.64 Compound of example 439 440 441442 T_(trans)./° C. 6.9 0.4 5.5 9.2 T trans. − Iso/deg. 18.4 10.2 15.820.3 ΔT/deg. 11.5 9.8 10.3 11.1 V₁₀₀(T trans. + 2)/V 35.5 35.5 38.5 36.5dV/dT(T trans. + 2)/V/deg. 0.9 1.0 1.0 0.9 dV*/dT(T trans. + 2)/deg.⁻¹0.03 0.03 0.02 0.02

TABLE 1q Use example 1.65 1.66 1.67 1.68 Compound of example 443 444 445446 T_(trans)./° C. 9.8 n.d. n.d. n.d. T trans. − Iso/deg. 19.8 n.d.n.d. n.d. ΔT/deg. 10.0 n.d. n.d. n.d. V₁₀₀(T trans. + 2)/V 38 n.d. n.d.n.d. dV/dT(T trans. + 2)/V/deg. 1 n.d. n.d. n.d. dV*/dT(T trans. +2)/deg.⁻¹ 0.03 n.d. n.d. n.d.Remarks:n.d.: not determined.

TABLE 1r Use example 1.69 1.70 1.71 1.72 Compound of example 447 448 449450 T_(trans)./° C. 12 25.4 n.d. 6.5 T trans. − Iso/deg. 17 32.6 n.d. 17ΔT/deg. 5 7.2 n.d. 10.5 V₁₀₀(T trans. + 2)/V 42 42.5 n.d. 39 dV/dT(Ttrans. + 2)/V/deg. 1.5 1.5 n.d. 2 dV*/dT(T trans. + 2)/deg.⁻¹ 0.04 0.03n.d. 0.05

TABLE 1s Use example 1.73 1.74 1.75 1.76 Compound of example 451 452 453454 T_(trans)./° C. 15 7.5 14.5 11.5 T trans. − Iso/deg. 23 18 22.5 20.5ΔT/deg. 8 10.5 8 9 V₁₀₀(T trans. + 2)/V 40 42 43 40 dV/dT(T trans. +2)/V/deg. 2 2 2 1.5 dV*/dT(T trans. + 2)/deg.⁻¹ 0.04 0.06 0.04 0.04

TABLE 1t Use example 1.77 1.78 1.79 1.80 Compound of example 455 456 457458 T_(trans)./° C. 23.5 15 9 3.3 T trans. − Iso/deg. 31 25.3 18.8 14.3ΔT/deg. 7.5 10.3 9.8 11 V₁₀₀(T trans. + 2)/V 37 39.5 41 43.5 dV/dT(Ttrans. + 2)/V/deg. 3 4.5 3 −1.5 dV*/dT(T trans. + 2)/deg.⁻¹ 0.08 0.120.07 −0.05Remarks:n.d.: not determined.

TABLE 1u Use example 1.81 1.82 1.83 1.84 Compound of example 459 460 461462 T_(trans)./° C. −2.6 1.9 22.1 3.9 T trans. − Iso/deg. 9.4 12.9 2915.1 ΔT/deg. 12 11 6.9 11.2 V₁₀₀(T trans. + 2)/V 42.5 39.5 41 43.5dV/dT(T trans. + 2)/V/deg. 1.5 1.0 0.8 0.9 dV*/dT(T trans. + 2)/deg.⁻¹0.05 0.03 0.02 0.03

TABLE 1v Use example 1.85 1.86 1.87 1.88 Compound of example 463 464 465466 T_(trans)./° C. 26.9 11.7 −1.1 n.d. T trans. − Iso/deg. 33.4 20.28.0 n.d. ΔT/deg. 6.5 8.5 9.1 n.d. V₁₀₀(T trans. + 2)/V 46 40 n.d. n.d.dV/dT(T trans. + 2)/V/deg. 1.5 1.0 n.d. n.d. dV*/dT(T trans. + 2)/deg.⁻¹0.03 0.02 n.d. n.d.

TABLE 1w Use example 1.89 1.90 1.91 1.92 Compound of example 467 468 469470 T_(trans)./° C. n.d. 28.1 7.5 n.d. T trans. − Iso/deg. n.d. 34.019.4 n.d. ΔT/deg. n.d. 5.9 12.1 n.d. V₁₀₀(T trans. + 2)/V n.d. 45 43.5n.d. dV/dT(T trans. + 2)/V/deg. n.d. 1.6 0.7 n.d. dV*/dT(T trans. +2)/deg.⁻¹ n.d. 0.03 0.02 n.d.Remarks:n.d.: not determined.

Use-Example 2

To the host mixture A various concentrations of the compound of example47 (also abbreviated as (P(O3)₂UQU-3O-T) are added.

The concentration of the compound of example 47 in the host mixture A isvaried from 3% over 5% and 7% to 15% The data are compiled in table 2.TABLE 2 Use example 2.1 2.2 2.3 2.4 Host mixture A P(O3)₂UQU-3O-T(Compound of example 47) c/% 3 5 7 15 T_(trans./° C.) 52 48 42 20 V₁₀₀(Ttrans. + 2)/V 115 123 127 96 dV/dT(T trans. + 2)/V/deg. 18 15 17 11+/−/V/deg. 2 5 5 3 dV*/dT(T trans. + 2)/deg.⁻¹ 0.16 0.13 0.13 0.11+/−/deg.⁻¹ 0.04 0.04 0.03 0.03Remarks:T_(trans.) is the transition temperature from the cholesteric phase intothe optically isotropic phase. It can be observed in electro-opticalcells with cross-polarisers.

There is no marked range with a flat dependency of the characteristicvoltages on the temperature, however there is a marked decrease of thetemperature dependency compared to the medium without the inventivecompound.

Use-Example 3

To the host mixture A various concentrations of the compound of example47 (P(O3)₂UQU-3O-T) are added in combination with various concentrationsof the chiral dopant R-5011 available from Merck KGaA.

The concentrations and the data are compiled in table 3. TABLE 3 Useexample 3.2 3.3 Host mixture A P(O3)₂UQU-3O-T (Compound of example 47)c/% 5 10 c(R-5011)/% 5  3 T_(trans./° C.) 18 n.d. T trans − Iso/deg. 26n.d. Flat T Range/deg. 8 n.d. V₁₀₀(T trans. + 2)/V 42 n.d. dV/dT(Ttrans. + 2)/V/deg. 1.5 n.d. (+/−)/V/deg. 1 n.d. dV*/dT(T trans. +2)/deg.⁻¹ 0.03 n.d. (+/−)/V/deg. 0.03 n.d.

In these systems a blue phase is observed and the temperature dependenceof the characteristic voltages is dramatically reduced, in fact, anextended range of temperatures with a flat temperature dependence isobtained.

Use-Example 4

A liquid crystal mixture, host mixture B, is realised consisting of:Mixture B Compound Concentration/ Abbreviation mass-% UZU-3A-N 15.0UZU-4A-N 5.6 GZU-3A-N 15.0 GZU-4A-N 15.0 GZU-4O-N 12.0 CUZU-2-N 11.0CUZU-3-N 11.0 CUZU-4-N 11.0 HP-3N.F 4.4 Σ 100.0

This mixture has the following properties:

Clearing point (T(N,I))/° C.: 22.5

To 85.0% of this mixture, host mixture B, 15% of the compound of example47 (P(O3)₂UQU-3O-T) is added and the properties of the resulting mixtureare determined. The concentrations and the data are compiled in table 4.

There is no marked range with a flat dependency of the characteristicvoltages on the temperature, however there is a marked decrease of thetemperature dependency compared to the medium without the inventivecompound. TABLE 4 Use example 4 Host mixture B P(O3)₂UQU-3O-T (Compoundof example 47) c/% 15 T_(trans./° C.) −10 T trans − Iso/deg. — Flat TRange/deg. — V₁₀₀(T trans. + 2)/V 59 dV/dT(T trans. + 2)/V/deg. 5.5+/−/V/deg. 2 dV*/dT(T trans. + 2)/deg.⁻¹ 0.10 +/−/deg.⁻¹ 0.04

Use-Example 5

A liquid crystal mixture, host mixture C, is realised consisting of:Mixture C Compound Concentration/ Abbreviation mass-% ME2N.F 12.0 ME3N.F15.0 ME4N.F 20.0 ME5N.F 20.0 HP-3N.F 10.0 HP-4N.F 10.0 HP-5N.F 8.0PCH-3N.F.F 5.0 Σ 100.0

This mixture has the following properties:

Clearing point (T(N,I))/° C.: 60.2

To 90% of this mixture, host mixture C, 5% of the compound of example 47(P(O3)₂UQU-3O-T) and 5% of the chiral dopant R-5011 are added and theproperties of the resulting mixture are determined. The concentrationsand the data are compiled in table 5. TABLE 5 Use example 5 Host mixtureC P(O3)₂UQU-3O-T (Compound of example 47) c/% 5 c(R-5011)/% 5T_(trans./° C.) 33 T trans − Iso/deg. 38 Flat T Range/deg. 5 V₁₀₀(Ttrans. + 2)/V 69 dV/dT(T trans. + 2)/V/deg. 0 +/−/V/deg. 2dV*/dT(Ttrans. + 2)/deg.⁻¹ 0.00 +/−/deg.⁻¹ 0.05

In these systems a blue phase is observed and the temperature dependenceof the characteristic voltages is dramatically reduced, in fact, anextended range of temperatures with a flat temperature dependence isobtained.

Use-Example 6

(The physical parameters given in the use-examples 6 to 8 are determinedaccording to “Merck Liquid Crystals, Physical Properties of LiquidCrystals”, Status November 1997, Merck KGaA, Germany)

A liquid crystal mixture is realised consisting which has the followingcomposition and properties. TABLE 6 Composition Compound Conc.Abbreviation /% BCH-3F.F 10.79 BCH-5F.F 8.99 ECCP-3OCF3 4.50 ECCP-5OCF34.50 CBC-33F 1.80 CBC-53F 1.80 CBC-55F 1.80 PCH-5F 8.99 PCH-6F 7.19PCH-7F 5.39 CCP-2OCF3 7.19 CCP-3OCF3 10.79 CCP-4OCF3 6.29 CCP-5OCF3 9.89P(O3)₂UQU-30-T 10.10 Σ 100.00 Properties T(N, I) = 65° C. n_(e) = 1.5688Δn = 0.0881 ε|| = 11.2

Use-Example 7

A liquid crystal mixture is realised, which has the followingcomposition and properties. TABLE 7 Composition Compound Conc.Abbreviation /% ME2N.F 10.8 ME3N.F 10.8 ME4N.F 10.8 ME5N.F 10.8 HP-3N.F4.5 HP-4N.F 4.5 HP-5N.F 4.5 CC-5-V 9.0 CCG-V-F 13.5 CCPC-33 3.6 CCPC-343.6 CCPC-35 3.6 P(O3)₂UQU-30-T 10.0 Σ 100.0 Properties T(N, I) = 51.2°C. n_(e) = 1.6229 Δn = 0.1227 ε|| = 58.8 Δε = +48.0

Use-Example 8

A liquid crystal mixture is realised, which has the followingcomposition and properties. TABLE 8 Composition Compound Conc.Abbreviation /% CCP-2F.F.F 10.8 CCP-3F.F.F 11.7 CCP-5F.F.F 7.2 CCP-2OCF39.0 CCP-3OCF3 7.2 CCP-4OCF3 6.3 CCP-5OCF3 7.2 CGU-2-F 10.8 CGU-3-F 10.8CGU-5-F 9.0 P(O3)₂UQU-30-T 10.0 Σ 100.0 Properties T(N, I) = 43.1° C.n_(e) = 1.5601 Δn = 0.0781 ε|| = 17.6

Use-Example 9

A liquid crystal mixture, host mixture D, is realised consisting of,Mixture D Compound Concentration/ Abbreviation mass-% AUUQU-3-N 11.7CUZU-3-N 10.6 CUZU-3-N 10.6 HP-3N.F 9.4 AUUQU-3-OT 11.8 AUUQU-3-F 10.6AUUQU-3-T 9.4 AUUQP-3-T 5.9 PUZU-3-F 10.6 PUZU-5-F 9.4 Σ 100.0

This mixture has the following properties:

Clearing point (T(N,I))/° C.: 99.0.

Use-Example 9.1

To this mixture, host mixture D, 10% of the compound of example 47(P(O3)₂UQU-3O-T) and 5% of the chiral dopant R-5011 are added, as shownin the following table, table 9, and the properties of the resultingmixture are determined. The results are compiled in table 9.

Use-Example 9.2

To the same mixture, host mixture D, now 5% of the compound of example47 (P(O3)₂UQU-3O-T), and 5% of the chiral dopant R-5011 and 2% of itsenantiomer S-5011 (equivalent to the addition of 3% of R-5011 and 4% ofthe racemate) are added, as shown in the following table, table 9, andthe properties of the resulting mixture are determined. The results arecompiled in table 9. TABLE 9 Use example 9.1 9.2 Host mixture DP(O3)₂UQU-3O-OT (Compound of example 47) c 10 5 c(R-5011)/% 5 c(S-5011)0 2 T_(trans./° C.) 31.0 49.0 T trans − Iso/deg. 33.0 Flat T Range/deg.13.5 7.0 V₁₀₀(T trans. + 2)/V 42 28

Use-Example 10 Use-Examples 10.1 and 10.2

To 85%, respectively 84%, of the host mixture D, used in example 9, 10%of the compound of example 1 (P(O3)₂UQU-3O-F) and the chiral dopantR-5011 is added in a concentration of 5% (Use-example 10.1),respectively of 4% (Use-example 10.2), and the properties of theresulting mixture are determined. The concentrations and the data arecompiled in table 10. TABLE 10 Use example 10.1 10.2 Host mixture DP(O3)₂UQU-3O-F (Compound of example 1) C/% 10 c(R-5011)/% 5 4T_(trans.)/° C. 33.0 42.0 T trans − Iso/deg. Flat T Range/deg. 12.5 9.0V₁₀₀(T trans. + 2)/V 43 35

Use-Example 11 Use-Example 11.1

To 85% of the host mixture D, used in Use-examples 9 and 10, 10% of thecompound of example 3 (P(O6)₂UQU-6O-F) and 5% of the chiral dopantR-5011 are added and the properties of the resulting mixture aredetermined. The concentrations and the data are compiled in table 11.TABLE 11 Use example 11.1 11.2 Host mixture D E P(O6)₂UQU-6O-F (Compoundof example 3) c/% 10 4 c(R-5011)/% 5 13 T_(trans.)/° C. 33.0 8.5 T trans− Iso/deg. Flat T Range/deg. 15.0 20.0 V₁₀₀(T trans. + 2)/V 41 60

Use-Example 11.2

A liquid crystal mixture, host mixture E, is realised consisting of:Mixture E Compound Concentration/ Abbreviation mass-% AUUQGU-3-F 9.0AUUQU-2-N 8.0 AUUQU-3-N 9.0 AUUQU-3-OT 10.0 AUUQU-3-T 10.0 AUUQU-3-F 9.0AUUQP-3-T 11.0 CUZU-3-N 7.0 CUZU-3-N 7.0 HP-3N.F 8.0 PUZU-3-F 5.0PUZU-5-F 9.0 UZU-3-N 9.0 Σ 100.0

To 83% of this mixture, host mixture E, 4% of the compound of example 3(P(O6)₂UQU-6O-F) and 13% of the chiral dopant R-5011 are added and theproperties of the resulting mixture are determined. The concentrationsand the data are compiled in table 11.

Use-Example 12

To 85% of the host mixture D, used in use-examples 0, 10 and 11.1, 10%of the compound of example 408 (P(O3)₂PQU-3O-F) and 5% of the chiraldopant R-5011 are added and the properties of the resulting mixture aredetermined. The concentrations and the data are compiled in table 12.TABLE 12 Use example 12 Host mixture D P(O3)₂PQU-3O-F (Compound ofexample 408) c/% 5 c(R-5011)/% 10 T_(trans.)/° C. 44 T trans − Iso/deg.Flat T Range/deg. 11.5 V₁₀₀(T trans. + 2)/V 32

Use-Example 13

A liquid crystal mixture, host mixture F, is realised consisting of:Mixture F Compound Concentration/ Abbreviation mass-% AUUQU-3-N 12.0AUZU-3-N 12.0 AUZU-5-N 12.0 GZU-3A-N 9.0 UZU-3A-N 9.0 AUUQU-3-OT 12.0AUUQU-3-T 8.0 AUUQU-3-F 8.0 PUZU-3-F 6.0 PUZU-5-F 12.0 Σ 100.0

Use-Examples 13.1 to 13.7

To this mixture, host mixture F, various concentrations of the compoundof example 47 (P(O3)₂UQU-3O-T) and various concentrations of the chiraldopant R-5011 are added and the properties of the resulting mixtures aredetermined. The concentrations and the data are compiled in tables 13aand 13b. TABLE 13a Use example 13.1 13.2 13.3 13.4 Host mixture FP(O3)₂UQU-3O-OT (Compound of example 47) c/% 5 7 c(R-5011) 3 5 7 5T_(trans.)/° C. 32.0 19.0 7.0 11.0 T trans − Iso/deg. Flat T Range/deg.4.0 8.5 12.5 11.5 V₁₀₀(T trans. + 2)/V 18 24 25 18.5

TABLE 13b Use example 13.5 13.6 13.7 Host mixture F P(O3)₂UQU-3O-OT(Compound of example 47) c/% 2 5 2 c(R-5011)/% 3 5 3 T_(trans.)/° C.12.0 4.0 3.5 T trans − Iso/deg. Flat T Range/deg. 14.5 13.5 18.5 V₁₀₀(Ttrans. + 2)/V 30 29.5 28

Use-Example 14

A liquid crystal mixture, host mixture G, is realised consisting of:Mixture G Compound Concentration/ Abbreviation mass-% AUUQU-2-F 11.0AUUQU-3-F 13.0 AUUQU-4-F 6.0 AUUQU-5-F 5.5 AUUQU-7-F 6.0 AUUQU-3-T 11.0AUUQU-3-OT 13.0 AUUQGU-3-F 7.0 PUZU-2-F 5.5 PUZU-3-F 11.0 PUZU-5-F 11.0Σ 100.0

This mixture has the following properties:

Clearing point (T(N,I))/° C., 75.0.

Use-Examples 14.1 and 14.2

To this mixture, host mixture G, alternatively 5% (use-example 14.1), 7%(use-example 14.2), and 10% (use-example 14.3), respectively, of thecompound of example 47 (P(O3)₂UQU-3O-T) and 5% of the chiral dopantR-5011 are added and the properties of the resulting mixtures aredetermined. The concentrations and the data are compiled in table 14.TABLE 14 Use example 14.1 14.2 14.3 Host mixture F P(O3)₂UQU-3O-OT(Compound of example 47) c/% 5 7 10 c(R-5011)/% 5 T_(trans.)/° C. 36.0n.d. 7.5 T trans − Iso/deg. Flat T Range/deg. 6.0 n.d. 13.0 V₁₀₀(Ttrans. + 2)/V 47 n.d. 41.5

Use-Example 15 Use-Examples 15.1 to 15.3

Three different liquid crystal mixtures, host mixtures H to I, arerealised consisting of: Mixture H Mixture I Compound CompoundConcentration/ Concentration/ Abbreviation Abbreviation mass-% mass-%PPYP-4N AUUQU-3-N 11.0 10.0 PTU-4O-N GZU-3A-N 10.0 10.0 PU-3-AN HP-3N.F8.0 15.0 PU-5-AN AUUQU-3-F 9.0 12.0 PGU-2-F AUUQGU-3-F 9.0 10.0 PGU-3-FCUZP-3-SF5 9.0 10.0 PGU-5-F PUZP-3-SF5 8.0 10.0 PGU-4-T AUZP-3-SF5 10.010.0 AUUQU-3-N AUUQP-2-SF5 9.0 4.0 MU-3-AN AUUQP-3-SF5 9.0 5.0 PTG-3-NAUUQP-5-SF5 8.0 4.0 Σ Σ 100.0 100.0 Mixture J Compound Concentration/Abbreviation mass-% AUUQGU-3-F 8.0 AUUQU-3-F 8.0 AUUQU-3-N 10.0AUUQU-3-OT 9.0 AUUQU-3-T 9.0 CUZU-2-N 10.0 CUZU-3-N 10.0 GZU-3A-N 10.0HP-2N.F 7.0 PUZU-2-F 6.0 PUZU-3-F 7.0 UUQU-3°-F 6.0 Σ 100.0

To each one of these mixtures, host mixtures H to K, the compound ofexample 47 (P(O3)₂UQU-3O-T) is addded together with the chiral dopantR-5011 in the concentrations given in table 15 and the properties of theresulting mixtures are determined. The results are compiled in table 15,too. TABLE 15 Use example 15.1 15.2 15.3 Host mixture H I JP(O3)₂UQU-3O-OT (Compound of example 47) c/% 5 6 4.5 c(R-5011) 5 7 10.0T_(trans.)/° C. 19.0 21.0 5.0 T trans − Iso/deg. Flat T Range/deg. 4.016.0 27.0 V₁₀₀(T trans. + 2)/V 45 56.5 55

Use-Example 16

A liquid crystal mixture, host mixture K, is realised consisting of:Mixture K Compound Concentration/ Abbreviation mass-% AUUQU-3-N 11.0CUZU-2-N 11.0 CUZU-3-N 11.0 GZU-3A-N 10.0 HP-2N.F 8.0 AUUQU-3-OT 9.0AUUQU-3-T 10.0 AUUQU-3-F 9.0 AUUQGU-3-F 9.0 PUZU-2-F 4.0 PUZU-3-F 8.0 Σ100.0

To this mixture, host mixture K, 5% of the compound of example 47(P(O3)₂UQU-3O-T) is addded together with 9% of the chiral dopantBO2C*H—C-5 (which is a homologue of S-5011 (also: BO2C*H—C-3) with ann-pentyl terminal chain instead of an n-propyl group and which has anHTP in MLC-6260, available from Merck KGaA, at 20° C. of −71.7 μm⁻¹) andthe property of the resulting mixture is determined. The results arecompiled in table 16. TABLE 16 Use example 16 Host mixture KP(O3)₂PQU-3O-T (Compound of example 47) c/% 5 c(BO2C*H-C-5)/% 9T_(trans.)/° C. 34.5 T trans − Iso/deg. Flat T Range/deg. 14.5 V₁₀₀(Ttrans. + 2)/V 35.5

Use-Example 17

A liquid crystal mixture, host mixture L, which is similar to hostmixture H used in use-example 15.1, is realised consisting of: Mixture LCompound Concentration/ Abbreviation mass-% PPYP-4N 10.0 PTU-4O-N 10.0PU-3-AN 13.0 PU-5-AN 13.0 PGU-2-F 10.0 PGU-3-F 12.0 PGU-5-F 10.0 PGU-4-T10.0 AUUQU-3-T 5.0 AUUQU-3-OT 5.0 MU-3-AN 5.0 PTG-3-N 7.0 Σ 100.0

To this mixture, host mixture L, 10% of the compound of example 47(P(O3)₂UQU-3O-T) is addded together with 5 of the chiral dopant R-5011and the property of the resulting mixture is determined. The results arecompiled in table 17. TABLE 17 Use example 17 Host mixture LP(O3)₂PQU-3O-T (Compound of example 47) c/% 10 c(R-5011)/% 5T_(trans.)/° C. 4.0 T trans − Iso/deg. Flat T Range/deg. 10.0 V₁₀₀(Ttrans. + 2)/V 53

1. Liquid crystal medium, characterised in that it comprises a stronglydielectrically positive liquid crystal component A, which comprises oneor more compounds of formula I

wherein a, b, c and d are independently of each other 0, 1 or 2, wherebya+b+c+d≦4; R¹¹ is hydrogen, an alkyl or alkoxy radical having from 1 to15 carbon atoms, wherein one or more methylene groups of said alkyl oralkoxy radical may be replaced independently of each other by —O—, —S—,—SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or —O—CO— such that oxygenand/or sulfur atoms are not linked directly to each other, said alkyl oralkoxy radical being unsubstituted or mono-substituted with a —CN groupor mono- or poly-substituted with halogen; or aryl, aryloxy, alkylaryl,alkylaryloxy, alkylarylalkyl, alkylarylalkoxy, cycloalkyl,cycloalkyloxy, cycloalkylalkenyloxy, alkylcycloalkyl, alkylcycloalkyloxyor alkylcycloalkylalkenyloxy, each with up to 15 carbon atoms, wherinsaid in radicals being unsubstituted or mono-substituted with a —CNgroup or mono- or poly-substituted with halogen one ore more ═CH— groupsmay be replaced independently of each other by ═N— and/or one more —CH₂—groups may be replaced independently of each other by —O—, —S—,—SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or —O—CO— such that nitrogenand oxygen and/or sulfur atoms are not linked directly to each other;L¹¹, L¹², L¹³ and L¹⁴ are, independently of each other, hydrogen, analkyl or alkoxy radical having from 1 to 15 carbon atoms, wherein one ormore methylene groups of said alkyl or alkoxy radical may be replacedindependently of each other by —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—, —C≡C—,—CO—O— and/or —O—CO— such that oxygen and/or sulfur atoms are not linkeddirectly to each other, said alkyl or alkoxy radical being unsubstitutedor mono-substituted with a —CN group or mono- or poly-substituted withhalogen; or aryl, aryloxy, alkylaryl, alkylaryloxy, alkylarylalkyl,alkylarylalkoxy, cycloalkyl, cycloalkyloxy, cycloalkylalkenyloxy,alkylcycloalkyl, alkylcycloalkyloxy or alkylcycloalkylalkenyloxy, eachwith up to 15 carbon atoms, wherin said in radicals being unsubstitutedor mono-substituted with a —CN group or mono- or poly-substituted withhalogen one ore more ═CH— groups may be replaced independently of eachother by ═N— and/or one more —CH₂— groups may be replaced independentlyof each other by —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or—O—CO— such that nitrogen and oxygen and/or sulfur atoms are not linkeddirectly to each other, whereby L¹³ and L¹⁴ are hydrogen, if at leastone of L¹¹ and L¹² is not hydrogen; L¹¹ and L¹² are hydrogen, if atleast one of L¹³ and L¹⁴ is not hydrogen; at least one of L¹¹, L¹², L¹³and L¹⁴ is not hydrogen; and L¹¹ and L¹² are not halogen at the sametime; X¹¹ is H, halogen, —CN, —NCS, —SF₅, —S—R^(z), —SO₂—R^(z), an alkylor alkoxy radical having from 1 to 15 carbon atoms, wherein one or moremethylene groups of said alkyl or alkoxy radical may be replacedindependently of each other by —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—, —C≡C—,—CO—O— and/or —O—CO— such that oxygen and/or sulfur atoms are not linkeddirectly to each other, said alkyl or alkoxy radical being unsubstitutedor mono-substituted with a —CN group or mono- or poly-substituted withhalogen; or aryl, aryloxy, alkylaryl, alkylaryloxy, alkylarylalkyl,alkylarylalkoxy, cycloalkyl, cycloalkyloxy, cycloalkylalkenyloxy,alkylcycloalkyl, alkylcycloalkyloxy or alkylcycloalkylalkenyloxy, eachwith up to 15 carbon atoms, wherin said in radicals being unsubstitutedor mono-substituted with a —CN group or mono- or poly-substituted withhalogen one ore more ═CH— groups may be replaced independently of eachother by ═N— and/or one more —CH₂— groups may be replaced independentlyof each other by —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or—O—CO— such that nitrogen and oxygen and/or sulfur atoms are not linkeddirectly to each other; R^(x) and R^(y) are independently of each otherhydrogen or an alkyl radical having from 1 to 7 carbon atoms; R^(z) isan alkyl radical having from 1 to 7 carbon atoms, said alkyl radicalbeing unsubstituted or mono- or poly-substituted with halogen; A¹¹, A¹²,A¹³ and A¹⁴ are independently of each other a ring of one of thefollowing formulas:

whereby each of A¹¹, A¹², A¹³ and A¹⁴ may be the same ring or twodifferent rings if present more than once; Y¹¹, Y¹², Y¹³ and Y¹⁴ areindependently of each other hydrogen, halogen, an alkyl or alkoxyradical having from 1 to 15 carbon atoms wherein one or more methylenegroups of said alkyl or alkoxy radical may be replaced independently ofeach other by —O—, —S—, —SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or—O—CO— such that oxygen and/or sulfa atoms are not linked directly toeach other, said alkyl or alkoxy radical being unsubstituted or mono- orpoly-substituted with halogen; or aryl, aryloxy, alkylaryl,alkylaryloxy, alkylarylalkyl, alkylarylalkoxy, cycloalkyl,cycloalkyloxy, cycloalkylalkenyloxy, alkylcycloalkyl, alkylcycloalkyloxyor alkylcycloalkylalkenyloxy, each with up to 15 carbon atoms, wherinsaid in radicals being unsubstituted or mono-substituted with a —CNgroup or mono- or poly-substituted with halogen one ore more ═CH— groupsmay be replaced independently of each other by ═N— and/or one more —CH₂—groups may be replaced independently of each other by —O—, —S—,—SiR^(x)R^(y)—, —CH═CH—, —C≡C—, —CO—O— and/or —O—CO— such that nitrogenand oxygen and/or sulfur atoms are not linked directly to each other; f,g, h and j are independently of each other 0, 1, 2 or 3; Z¹¹, Z¹², Z¹³and Z¹⁴ are independently of each other a single bond, —CH₂CH₂—,(—CH₂CH₂—)₂, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—,—CH═CF—, —C≡C—, —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—, —CO—O— or —O—CO— wherebyeach of Z¹¹, Z¹², Z¹³ and Z¹⁴ may have the same or a different meaningif present more than once.
 2. Liquid crystal medium according to claim1, characterised in that, it comprises one or more compounds of formulaI-1

wherein the parameters have the meaning given in claim
 1. 3. Liquidcrystal medium according to claim 2, characterised in that, it comprisesone or more compounds of formula I-1 given in claim 2 wherein R¹, R¹²and R¹³, independently of each other, are n-alkyl or n-alkoxy with 1 to20 C-atoms, alkenyl, alkenyloxy or alkoxyalkyl with 2 to 20 C-atoms orCN, NCS, halogen, halogenated alkyl, alkenyl or alkoxy, L¹¹, L¹², Y¹¹and Y¹², independently of each other, are H, halogen, CN, NCS,halogenated alkyl, alkenyl or alkoxy and X¹¹ is H, halogen or Cl, CN,NCS, SF₅, —SCF₃, —SO₂CF₃, —SO₂C₂F₅, —SO₂C₄F₉, halogenated alkyl, alkenylor alkoxy.
 3. Liquid crystal medium according to claim 1, characterisedin that the dielectrically positive component B comprises one or morecompounds of formula II

wherein n² is 0, 1 or 2, R² has the meaning given for R¹¹ under formulaI in claim 1, Z²¹ and Z²², independently of each other, are a singlebond, —CH₂CH₂—, (—CH₂CH₂—)₂, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—,—CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—, —CO—O—or —O—CO— whereby each of Z²² may have the same or a different meaningif present twice,

 each, independently of each other, are

 whereby

 is also

X² is CN, NCS, SF₅, SO₂CF₃, CF₃, OCF₃, F or Cl.
 4. Compound of formulaI-1

wherein R¹¹, R¹² and R¹³, independently of each other, are n-alkyl orn-alkoxy with 1 to 20 C-atoms, alkenyl, alkenyloxy or alkoxyalkyl with 2to 20 C-atoms, or CN, NCS, halogen, halogenated alkyl, alkenyl oralkoxy, L¹¹, L¹², Y¹¹ and Y¹², independently of each other, are H,halogen, CN, NCS, unsubstituted or halogenated alkyl, alkenyl or alkoxy,and X¹¹ is H, halogen, CN, NCS, SF₅, SO₂CF₃, halogenated alkyl, alkenylor alkoxy, preferably mono-, di- or oligo-fluorinated alkyl, alkenyl oralkoxy.
 5. Compound according to claim 4, characterised in that R¹¹, R¹²and R¹³, independently of each other, are n-alkyl or n-alkoxy with 1 to7 C-atoms preferably 2 to 5 C-atoms, alkenyl, alkenyloxy or alkoxyalkylwith 2 to 7 C atoms or CN, NCS, halogen, preferably F, Cl, halogenatedalkyl, alkenyl or alkoxy, L¹¹, L¹², Y¹¹ and Y¹², independently of eachother, are H, halogen, CN, NCS, unsubstituted or halogenated alkyl,alkenyl or alkoxy, preferably mono-, di- or oligo-fluorinated alkyl,alkenyl or alkoxy and X¹¹ is H, halogen, preferably F or Cl, CN, NCS,SF₅, SO₂CF₃, unsubstituted or halogenated alkyl, alkenyl or alkoxy,preferably mono-, di- or oligo-fluorinated alkyl, alkenyl or alkoxy. 6.Compound according to claim 4, characterised in that R¹¹, R¹² and R¹³are identical to each other.
 7. Compound according to claim 4,characterised in that R¹¹, R¹² and R¹³, independently of each other,n-alkoxy with 1 to 7 C-atoms or alkenyloxy with 2 to 7 C-atoms. 8.Compound according to claim 1, characterised in that X¹¹ is F, Cl, CN,NCS, SF₅, SO₂CF₃, F, CF₃ or OCF₃.
 9. Compound according to claim 4,characterised in that at least one of L¹¹ and L¹² is F and at least oneof Y¹¹ and Y¹² is F and the others are, independently of each other, Hor F.
 10. Liquid crystal display, characterised in that it comprises aliquid crystal medium according to claim
 1. 11. Liquid crystal displayaccording to claim 10, characterised in that it is operated or operableat a temperature at which mesogenic control medium is in an opticallyisotropic state.
 12. Use of a liquid crystal medium according to claim 1in an electro-optical display.
 13. Use of a compound according to claim5 in a liquid crystal mixture.
 14. Use of a compound according to claim5 in an electro-optical display.
 15. Use of a liquid crystal mediumaccording to claim 1 in an electro-optical display.
 16. Liquid crystaldisplay, characterised in that it comprises a liquid compound accordingto claim 4.